Green Ultrasound-Assisted Synthesis of Rare-Earth-Based MOFs.

Rare-earth (RE)-based metal organic frameworks (MOFs) are quickly gaining popularity as flexible functional materials in a variety of technological fields. These MOFs are useful for more than just conventional uses like gas sensors and catalyst materials; in fact, they also show significant promise in emerging technologies including photovoltaics, optical, and biomedical applications. Using yttrium and europium as ionic host centres and dopants, respectively, and 1,3,5-benzenetricarboxylic acid (H3-BTC) as an organic linker, we describe a simple and green approach for the fabrication of RE-MOFs. Specifically, Y-BTCs and Eu-doped Y-BTCs MOFs have been synthesised in a single step using an eco-friendly method that makes use of ultrasound technology. To establish a correlation between the morphological and structural properties and reaction conditions, a range of distinct reaction periods has been employed for the synthetic processes. Detailed analyses of the synthesised samples through powder X-ray diffraction (PXRD), field emission scanning electron microscopy (FE-SEM), and Fourier-transform infrared spectroscopy (FT-IR) have confirmed the phase formation. Furthermore, thermal analyses such as thermogravimetric analysis (TGA) have been employed to evaluate the thermal stability and structural modifications of the Y-BTC and Eu-doped Y-BTC samples. Finally, the luminescent properties of the synthesised samples doped with Eu3+ have been assessed, providing an evaluation of their characteristics. As a proof of concept, an Eu-doped Y-BTC sample has been applied for the sensing of nitrobenzene as a molecule test of nitro derivatives.

Metalorganic Chemical Vapor Deposition Approach to the Synthesis of Perovskite BaCeO3 and BaCe0.8Y0.2O3 Thin Films.

In the present energetic scenario, the development of materials with high potentiality in the technological fields of energy conversion processes, production and storage of hydrogen, are of great interest in the scientific community. In particular, we report for the first time the fabrication of crystalline and homogeneous barium-cerate-based materials in the form of thin films on various substrates. Starting from the ß-diketonate precursor sources Ce(hfa)3diglyme, Ba(hfa)2tetraglyme and Y(hfa)3diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetylacetone; diglyme = bis(2-methoxyethyl)ether; tetraglyme = 2,5,8,11,14-pentaoxapentadecane), a metalorganic chemical vapor deposition (MOCVD) approach has been successfully applied to the fabrication of BaCeO3 and doped BaCe0.8Y0.2O3 systems in the form of thin films. Structural, morphological and compositional analyses allowed for an accurate determination of the properties of deposited layers. The present approach represents a simple, easily scalable, and industrially appealing process for the production of compact and homogeneous barium cerate thin films.

A Low Temperature Growth of Cu2O Thin Films as Hole Transporting Material for Perovskite Solar Cells.

Copper oxide thin films have been successfully synthesized through a metal-organic chemical vapor deposition (MOCVD) approach starting from the copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate), Cu(tmhd)2, complex. Operative conditions of fabrication strongly affect both the composition and morphologies of the copper oxide thin films. The deposition temperature has been accurately monitored in order to stabilize and to produce, selectively and reproducibly, the two phases of cuprite Cu2O and/or tenorite CuO. The present approach has the advantages of being industrially appealing, reliable, and fast for the production of thin films over large areas with fine control of both composition and surface uniformity. Moreover, the methylammonium lead iodide (MAPI) active layer has been successfully deposited on the ITO/Cu2O substrate by the Low Vacuum Proximity Space Effusion (LV-PSE) technique. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and atomic force microscopy (AFM) analyses have been used to characterize the deposited films. The optical band gap (Eg), ranging from 1.99 to 2.41 eV, has been determined through UV-vis analysis, while the electrical measurements allowed to establish the p-type conductivity behavior of the deposited Cu2O thin films with resistivities from 31 to 83 Ω cm and carrier concentration in the order of 1.5-2.8 × 1016 cm-3. These results pave the way for potential applications of the present system as a hole transporting layer combined with a perovskite active layer in emergent solar cell technologies.

Sodium ß-Diketonate Glyme Adducts as Precursors for Fluoride Phases: Synthesis, Characterization and Functional Validation.

Very few sodium complexes are available as precursors for the syntheses of sodium-based nanostructured materials. Herein, the diglyme, triglyme, and tetraglyme (CH3O(CH2CH2O)nCH3, n = 2-4) adducts of sodium hexafluoroacetylacetonate were synthesized in a single-step reaction and characterized by IR spectroscopy, 1H, and 13C NMR. Single-crystal X-ray diffraction studies provide evidence of the formation of the ionic oligomeric structure [Na4(hfa)6]2-•2[Na(diglyme2]+ when the diglyme is coordinated, while a mononuclear seven-coordinated complex Na(hfa)•tetraglyme is formed with the tetraglyme. Reaction with the monoglyme (CH3OCH2CH2OCH3) does not occur, and the unadducted polymeric structure [Na(hfa)]n forms, while the triglyme gives rise to a liquid adduct, Na(hfa)•triglyme•H2O. Thermal analysis data reveal great potentialities for their applications as precursors in metalorganic chemical vapor deposition (MOCVD) and sol-gel processes. As a proof-of-concept, the Na(hfa)•tetraglyme adduct was successfully applied to both the low-pressure MOCVD and the sol-gel/spin-coating synthesis of NaF films.

Synthesis, characterization and photocatalytic properties of nanostructured lanthanide doped ß-NaYF4/TiO2 composite films.

The photocatalytic approach is known to be one of the most promising advanced oxidation processes for the tertiary treatment of polluted water. In this paper, ß-NaYF4/TiO2 composite films have been synthetized through a novel sol-gel/spin-coating approach using a mixture of ß-diketonate complexes of Na and Y, and Yb3+, Tm3+, Gd3+, Eu3+ as doping ions, together with the TiO2 P25 nanoparticles. The herein pioneering approach represents an easy, straightforward and industrially appealing method for the fabrication of doped ß-NaYF4/TiO2 composites. The effect of the doped ß-NaYF4 phase on the photocatalytic activity of TiO2 for the degradation of methylene blue (MB) has been deeply investigated. In particular, the upconverting TiO2/ß-NaYF4: 20%Yb, 2% Gd, x% Tm (x = 0.5 and 1%) and the downshifting TiO2/ß-NaYF4: 10% Eu composite films have been tested on MB degradation both under UV and visible light irradiation. An improvement up to 42.4% in the degradation of MB has been observed for the TiO2/ß-NaYF4: 10% Eu system after 240 min of UV irradiation.

Journey of a molecule from the solid to the gas phase and vice versa: direct estimation of vapor pressure of alkaline-earth metalorganic precursors for atmospheric pressure vapor phase deposition of fluoride films.

Atmospheric pressure (AP) vapor phase processes such as spatial atomic layer deposition (S-ALD) and AP-metalorganic chemical vapor deposition (AP-MOCVD) are becoming increasingly appealing for their use in a variety of academic and industrial applications. Evaluation of precursor vapour pressures is crucial for their application in AP processes and to this aim the Langmuir equation has been applied as a simple and straightforward method for estimating the vapor pressure and vaporization enthalpy of various metalorganic precursors. Using benzoic acid as a calibration reference, the vapour pressure-temperature curves for several alkaline-earth ß-diketonate fluorinated compounds, with molecular formula "M(hfa)2·L" (with M = Mg, Ca, Sr, Ba; Hhfa = 1,1,1,5,5,5-hexafluoroacetylacetone and L = diglyme, triglyme, and tetraglyme) are derived from their termogravimetric curves. Thus, the enthalpy of vaporization of all complexes has been estimated using the Clausius-Clapeyron equation. As a proof of concept, preliminary results on the use of [Mg(hfa)2·2H2O]·2diglyme and [Ca(hfa)2·diglyme·H2O] or [Ca(hfa)2·triglyme] as precursors for AP-MOCVD deposition of MgF2 and CaF2 in the form of thin films are presented. This approach may be used to easily determine vapor pressures of complexes and thus evaluate "a priori" the suitability of a compound as precursor for AP-MOCVD and/or spatial ALD.

A Facile One-Pot Approach to the Synthesis of Gd-Eu Based Metal-Organic Frameworks and Applications to Sensing of Fe3+ and Cr2O72- Ions.

Gadolinium metal-organic frameworks (Gd-MOFs) and Eu-doped Gd-MOFs have been synthesized through a one-pot green approach using commercially available reagents. The 1,4-benzenedicarboxylic acid (H2-BDC) and 2,6-naphthalenedicarboxylic acid (H2-NDC) were chosen as ditopic organic linkers to build the 3D structure of the network. The Gd-MOFs were characterized using powder X-ray diffraction (XRD), FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM) and N2 adsorption-desorption analysis. The Gd-MOF structures were attributed comparing the XRD patterns, supported by the FT-IR spectra, with data reported in the literature for Ln-MOFs of similar lanthanide ionic radius. FE-SEM characterization points to the effect of the duration of the synthesis to a more crystalline and organized structure, with grain dimensions increasing upon increasing reaction time. The total surface area of the MOFs has been determined from the application of the Brunauer-Emmett-Teller method. The study allowed us to correlate the processing conditions and ditopic linker dimension to the network surface area. Both Gd-MOF and Eu-doped Gd-MOF have been tested for sensing of the inorganic ions such as Fe3+ and Cr2O72-.

Novel sol-gel fabrication of Yb3+/Tm3+ co-doped ß-NaYF4 thin films and investigation of their upconversion properties.

An innovative sol-gel process, using a mixture of Na(hfa)·tetraglyme and RE(hfa)3·diglyme (RE = Y, Yb, Tm) complexes, has been optimized to produce upconverting ß-NaYF4:Yb3+/Tm3+ thin films. The X-ray diffraction (XRD) analysis confirms that the new sol-gel preparation route yields reproducibly and selectively the hexagonal Na(Y1.5Na0.5)F6 structure (ß-NaYF4) without any impurity phases, since no peaks of the cubic NaYF4, YOF, Y2O3 or NaF phases were observed. This final goal has been achieved through an accurate optimization of the operative parameters such as the molar ratio of the precursor mixture, the aging time of the sol, the spin coating procedure and the annealing temperature. Field-emission scanning electron microscopy (FE-SEM) images indicate that the morphology of the surfaces, grain dimensions and thickness are strongly related to the processing parameters, with the hexagonal phase films having a very uniform morphology. Energy dispersive X-ray (EDX) analyses established the film composition in terms of dopant ions, which are responsible for the upconverting properties of the material. Luminescence measurements under laser excitation at 980 nm confirmed the promising upconversion properties of the ß-NaYF4:Yb3+/Tm3+ films.