Search results for: S. Agnello

Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas

Abstract:

Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.

Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis

Procedia PDF Downloads 18

Authors: Simone Dell'Agnello

Abstract:

There are laser retroreflectors on the Moon and no laser retroreflectors on Mars. Here we describe the design, construction, qualification and imminent deployment of next-generation, optimized laser retroreflectors on the Moon and on Mars (where they will be the first ones). These instruments are positioned by time-of-flight measurements of short laser pulses, the so-called 'laser ranging' technique. Data analysis is carried out with PEP, the Planetary Ephemeris Program of CfA (Center for Astrophysics). Since 1969 Lunar Laser Ranging (LLR) to Apollo/Lunokhod laser retro-reflector (CCR) arrays supplied accurate tests of General Relativity (GR) and new gravitational physics: possible changes of the gravitational constant Gdot/G, weak and strong equivalence principle, gravitational self-energy (Parametrized Post Newtonian parameter beta), geodetic precession, inverse-square force-law; it can also constraint gravitomagnetism. Some of these measurements also allowed for testing extensions of GR, including spacetime torsion, non-minimally coupled gravity. LLR has also provides significant information on the composition of the deep interior of the Moon. In fact, LLR first provided evidence of the existence of a fluid component of the deep lunar interior. In 1969 CCR arrays contributed a negligible fraction of the LLR error budget. Since laser station range accuracy improved by more than a factor 100, now, because of lunar librations, current array dominate the error due to their multi-CCR geometry. We developed a next-generation, single, large CCR, MoonLIGHT (Moon Laser Instrumentation for General relativity high-accuracy test) unaffected by librations that supports an improvement of the space segment of the LLR accuracy up to a factor 100. INFN also developed INRRI (INstrument for landing-Roving laser Retro-reflector Investigations), a microreflector to be laser-ranged by orbiters. Their performance is characterized at the SCF_Lab (Satellite/lunar laser ranging Characterization Facilities Lab, INFN-LNF, Frascati, Italy) for their deployment on the lunar surface or the cislunar space. They will be used to accurately position landers, rovers, hoppers, orbiters of Google Lunar X Prize and space agency missions, thanks to LLR observations from station of the International Laser Ranging Service in the USA, in France and in Italy. INRRI was launched in 2016 with the ESA mission ExoMars (Exobiology on Mars) EDM (Entry, descent and landing Demonstration Module), deployed on the Schiaparelli lander and is proposed for the ExoMars 2020 Rover. Based on an agreement between NASA and ASI (Agenzia Spaziale Italiana), another microreflector, LaRRI (Laser Retro-Reflector for InSight), was delivered to JPL (Jet Propulsion Laboratory) and integrated on NASA’s InSight Mars Lander in August 2017 (launch scheduled in May 2018). Another microreflector, LaRA (Laser Retro-reflector Array) will be delivered to JPL for deployment on the NASA Mars 2020 Rover. The first lunar landing opportunities will be from early 2018 (with TeamIndus) to late 2018 with commercial missions, followed by opportunities with space agency missions, including the proposed deployment of MoonLIGHT and INRRI on NASA’s Resource Prospectors and its evolutions. In conclusion, we will extend significantly the CCR Lunar Geophysical Network and populate the Mars Geophysical Network. These networks will enable very significantly improved tests of GR.

Keywords: general relativity, laser retroreflectors, lunar laser ranging, Mars geodesy

Procedia PDF Downloads 241