Synthesis, Structure and (Photo)Catalytic Behavior of Ce-MOFs Containing Perfluoroalkylcarboxylate Linkers: Experimental and Theoretical Insights.

Cerium-based Metal-Organic frameworks (Ce-MOFs) are attracting increasing interest due to their similar structural features to zirconium MOFs. The redox behavior of Ce(III/IV) adds a range of properties to the compounds. Recently, perfluorinated linkers have been used in the synthesis of MOFs to introduce new characteristic into the structure. We report the synthesis and structural characterization of Ce(IV)-based MOFs constructed using two perfluorinated alkyl linkers. Their structure, based on hexanuclear Ce6O4(OH)4 12+ clusters linked to each other by the dicarboxylate ions, has been solved ab-initio from X-ray powder diffraction data and refined by the Rietveld method. The crystallization kinetics and the MOF formation mechanism was also invesitigated by Synchrotron radiation with XAS spectroscopies (EXAFS and XANES). The MOFs present the same fcu cubic topology as observed in MOF-801 and UiO-66, and they showed good stability in water at different pH conditions. The electronic structure of these MOFs has been studied by DFT calculations in order to obtain insights into the density of states structure of the reported compounds, resulting in band gaps in the range of 2.8-3.1 eV. Their catalytic properties were tested both thermally and under visible light irradiation for the degradation of methyl orange (MO) dye.

Discovery and In Situ Crystallization Studies of Cerium-Based Metal-Organic Frameworks with V-Shaped Linker Molecules.

We report the discovery and characterization of two porous Ce(III)-based metal-organic frameworks (MOFs) with the V-shaped linker molecules 4,4'-sulfonyldibenzoate (SDB2-) and 4,4'-(hexafluoroisopropylidene)bis(benzoate) (hfipbb2-). The compounds of framework composition [Ce2(H2O)(SDB)3] (1) and [Ce2(hfipbb)3] (2) were obtained by using a synthetic approach in acetonitrile that we recently established. Structure determination of 1 was accomplished from 3D electron diffraction (3D ED) data, while 2 could be refined against powder X-ray diffraction (PXRD) data using the crystal structure of an isostructural La-MOF as the starting model. Their framework structures consist of chain-like inorganic building units (IBUs) or hybrid-BUs that are interconnected by the V-shaped linker molecules to form framework structures with channel-type pores. The composition of both compounds was confirmed by PXRD, elemental analysis, as well as NMR and IR spectroscopy. Interestingly, despite the use of (NH4)2[CeIV(NO3)6] in the synthesis, cerium ions in both MOFs occur exclusively in the + III oxidation state as determined by X-ray absorption near edge structure (XANES) and X-ray photoelectron spectroscopy (XPS). Thermal analyses reveal remarkably high thermal stabilities of ≥400 °C for the MOFs. Initial N2 sorption measurements revealed the peculiar sorption behavior of 2 which prompted a deeper investigation by Ar and CO2 sorption experiments. The combination with nonlocal density functional theory (NL-DFT) calculations adds to the understanding of the nature of the different pore diameters in 2. An extensive quasi-simultaneous in situ XANES/XRD investigation was carried out to unveil the formation of Ce-MOFs during the solvothermal syntheses in acetonitrile. The crystallization of the two Ce(III)-MOFs presented herein as well as two previously reported Ce(IV)-MOFs, all obtained by a similar synthetic approach, were studied. While the XRD patterns show time-dependent MOF crystallization, the XANES data reveal the presence of Ce(III) intermediates and their subsequent conversion to the MOFs. The addition of acetic acid in combination with the V-shaped linker molecule was identified as the crucial factor for the formation of the crystalline Ce(III/IV)-MOFs.

The armoured cuticle of the black soldier fly Hermetia illucens.

We characterise in detail the larval and pupal cuticle of the black soldier fly Hermetia illucens L. (Diptera: Stratiomyidae), a key insect species in circular economy. In particular, we focus on ultrastructure using scanning and transmission electron microscopy, material characterization and composition (elements and minerals) with confocal laser scanning microscope, energy dispersive X-ray microanalysis, powder X-ray diffraction and mechanical properties with nanoindentation measurements. Calcium carbonate crystallizes on the epicuticle as blocks of calcite in the pupal cuticle. Calcium carbonate granules are stored in two specialised Malpighian tubules. CaCO3 is already present in the cuticle of young larval instars, but it is mainly in the form of amorphous calcium carbonate while the amount of calcite increases during larval development. The presence of calcite leads to cuticle hardening. Larval and pupal cuticles contain large amounts of resilin which guarantee cuticle flexibility.

Recent advances in the chemistry and applications of fluorinated metal-organic frameworks (F-MOFs).

Metal-organic frameworks are a class of porous crystalline materials based on the ordered connection of metal centers or metal clusters by organic linkers with comprehensive functionalities. The interest in these materials is rapidly moving towards their application in industry and real life. In this context, cheap and sustainable synthetic strategies of MOFs with tailored structures and functions are nowadays a topic widely studied from different points of view. In this review, fluorinated MOFs (F-MOFs) and their applications are investigated. The principal aim is to provide an overview of the structural features and the main application of MOFs containing fluorine atoms both as anionic units or as coordinating elements of more complex inorganic units and, therefore, directly linked to the structural metals or as part of fluorinated linkers used in the synthesis of MOFs. Herein we present a review of F-MOFs reported in the recent literature compared to benchmark compounds published over the last 10 years. The compounds are discussed in terms of their structure and properties according to the aforementioned classification, with an insight into the different chemical nature of the bonds. The application fields of F-MOFs, especially in sustainability related issues, such as harmful gas sorption and separation, will also be discussed. F-MOFs are compounds containing fluorine atoms in their framework and they can be based on: (a) fluorinated metallic or semi-metallic anionic clusters or: (b) fluorinated organic linkers or (c) eventually containing both the building blocks. The nature of a covalent C-F bond in terms of length, charge separation and dipole moment sensibly differs from that of a partly ionic M-F (M = metal) one so that the two classes of materials (points a and b) have different properties and they find various application fields. The study shows how the insertion of polar M-F and C-F bonds in the MOF structure may confer several advantages in terms of interaction with gaseous molecules and the compounds can find application in gas sorption and separation. In addition, hydrophobicity tends to increase compared to non-fluorinated analogues, resulting in an overall improvement in moisture stability.

Synthesis, Crystal Structure, and Photocatalytic Properties of Two Isoreticular Ce(IV)-MOFs with an Infinite Rod-Shaped Inorganic Building Unit.

The use of the V-shaped linker molecules 4,4'-oxydibenzoic acid (H2ODB) and 4,4'-carbonyldibenzoic acid (H2CDB) led to the discovery of two isoreticular Ce(IV)-based metal-organic frameworks (MOFs) of composition [CeO(H2O)(L)], L = ODB2-, CDB2-, denoted CAU-58 (CAU = Christian-Albrechts-University). The recently developed Ce-MOF synthesis approach in acetonitrile as the solvent proved effective in accessing Ce(IV)-MOF structures with infinite rod-shaped inorganic building units (IBUs) and circumventing the formation of the predominantly observed hexanuclear [Ce6O8] cluster. For the structure determination of the isoreticular MOFs, three-dimensional electron diffraction (3D ED) and powder X-ray diffraction (PXRD) data were used in combination with density functional theory (DFT) calculations. [CeO(H2O)(CDB)] shows reversible H2O adsorption by stirring in water and thermal treatment at 190 °C, which leads to a unit cell volume change of 11%. The MOFs feature high thermal stabilities (T > 290 °C), which exceed those of most Ce(IV)-MOFs and can be attributed to the infinite rod-shaped IBU. Surface and bulk oxidation states of the cerium ions were analyzed via X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge spectroscopy (XANES). While Ce(III) ions are observed by the highly surface-sensitive XPS method, the bulk material contains predominantly Ce(IV) ions according to XANES. Application of the MOFs as catalysts for the catalytic degradation of methyl orange in aqueous solutions was also studied. While degradation activity for both MOFs was observed, only CAU-58-ODB revealed enhanced photocatalytic activity under ultraviolet (UV) light. The photocatalytic mechanism likely involves a ligand-to-metal charge transfer (LMCT) from the linkers to the Ce(IV) centers. Analyses by XANES and inductively coupled plasma-optical emission spectroscopy (ICP-OES) demonstrate that leaching of Cerium ions as well as partial reduction of Ce(IV) to Ce(III) takes place during catalysis. At the same time, PXRD data confirm the structural stability of the remaining MOF catalysts.