Synthesis, Characterization and Photophysical Properties of a New Family of Rare-earth Cluster-based Metal-organic Frameworks.

In this work, nine new rare-earth metal-organic frameworks (RE-MOFs, where RE = Lu(III), Yb(III), Tm(III), Er(III), Ho(III), Dy(III), Tb(III), Gd(III), and Eu(III)) isostructural to Zr-MOF-808 are synthesized, characterized, and studied regarding their photophysical properties. Materials with high crystallinity and surface area are obtained from a reproducible synthetic procedure that involves the use of two fluorinated modulators. At the same time, these new RE-MOFs display tunable photoluminescent properties due to efficient linker-to-metal energy transfer promoted by the antenna effect, resulting in a series of RE-MOFs displaying lanthanoid-based emissions spanning the visible and near-infrared regions of the electromagnetic spectrum.

Engineering the Surface Chemistry and Morphology of Polymeric Carbon Nitrides Towards Greener Heterogeneous Catalysts for Biodiesel Synthesis.

Biodiesel remains one of the most promising alternatives to replace fossil fuel-derived petrodiesel. Nonetheless, conventional biodiesel synthesis relies on homogeneous alkali-based catalysts that involve long and tedious purification steps , increasing biodiesel production costs. Heterogeneous catalysts have emerged as promising alternatives to circumvent these drawbacks, as they can easily be recovered and reused. Herein, polymeric carbon nitride dots and nanosheets are synthesized through a solid-phase reaction between urea and sodium citrate. Their morphology and surface chemistry are tuned by varying the precursor's ratio, and the materials are investigated as catalysts in the transesterification reaction of canola oil to biodiesel. A conversion of > 98% is achieved using a 5 wt% catalyst loading, oil to methanol ratio of 1:36 at 90 °C for 4 h, with the performance maintained over at least five reuse cycles. In addition, the effect of the transesterification reaction parameters on the reaction kinetics is evaluated, which follows a pseudo-first-order (PFO) regime. Combined with a deep understanding of the catalyst's surface, these results have allowed us to propose a reaction mechanism similar to the one observed for homogenous alkali catalysts. These carbon nitride-based nanoparticles offer a metal-free and cost-effective alternative to conventional homogeneous and metal-based heterogeneous catalysts.

Adsorptive removal of iodate oxyanions from water using a Zr-based metal-organic framework.

A Zr6-based metal-organic framework (MOF), MOF-808, is investigated for the adsorptive removal of IO3- from aqueous solutions, due to its high surface area and abundance of open metal sites. The uptake kinetics, adsorption capacity and binding mode are studied, showing a maximum uptake capacity of 233 mg g-1, the highest reported by any material.

Unravelling the synthesis of a rare-earth cluster-based metal-organic framework with spn topology.

Y-CU-45, an analogue of Zr-MOF-808, is synthesized for the first time. Several reaction conditions are tested demonstrating that two fluorinated modulators are required for a reproducible synthesis yielding high quality material. Y-CU-45 shows high crystallinity and surface area, shining light on the potential for rare-earth cluster-based MOFs with open metal sites.

Remodelling a shp: Transmetalation in a Rare-Earth Cluster-Based Metal-Organic Framework.

Postsynthetic modification of metal-organic frameworks (MOFs) is an important strategy for accessing MOF analogues that cannot be easily synthesized de novo. In this work, the rare-earth (RE) cluster-based MOF Y-CU-10 with shp topology was modified through transmetalation using a series of RE ions, including La(III), Nd(III), Eu(III), Tb(III), Er(III), Tm(III), and Yb(III). In all cases, metal exchange higher than 70% was observed, with reproducible results. All transmetalated materials were fully characterized and compared to the parent MOF Y-CU-10 with regard to crystallinity, surface area, and morphology. Additionally, single-crystal X-ray diffraction measurements were performed to provide further evidence of transmetalation occurring in the nonanuclear cluster nodes of the MOF.

Synthetic approaches for accessing rare-earth analogues of UiO-66.

Rare-earth (RE) analogues of UiO-66 with non-functionalised 1,4-benzenedicarboxylate linkers are synthesised for the first time, and a series of synthetic approaches is provided to troubleshoot the synthesis. RE-UiO-66 analogues are fully characterised, and demonstrate a high degree of crystallinity, high surface area and thermal stability, consistent with the UiO-66 archetype.

Efficient activation of peroxymonosulfate by composites containing iron mining waste and graphitic carbon nitride for the degradation of acetaminophen.

In this work, the potential to use an iron mining waste (IW), rich in α-Fe2O3 and α-FeOOH, for the development of composites based on graphitic carbon nitride (CN) is demonstrated. These materials were synthesized through a simple thermal treatment at 550 °C of a mixture containing melamine and different IW mass percentages, giving rise to the catalysts xIWCN (where x is related to the initial mass percentage of IW). The iron phases of the precursor were partially transformed throughout the formation of the composites, in such a way that a mixture of α-Fe2O3 and γ-Fe2O3 was observed in their final composition. Furthermore, structural defects were produced in the carbonaceous matrix of the materials, causing the fragmentation of g-C3N4 and an increase of surface area. The catalytic activities of these composites were evaluated in reactions of peroxymonosulfate activation for the degradation of paracetamol. Among these materials, the composite 20IWCN showed the best catalytic activity, being able to degrade almost 90 % of the total paracetamol in only 20 min of reaction. This catalyst also demonstrated high chemical stability, being successfully utilized in five consecutive reaction cycles, with negligible iron leaching.