Decomposition Process of Carboxylate MOF HKUST-1 Unveiled at the Atomic Scale Level
HKUST-1 is a metal-organic framework (MOF) which plays a significant role both in applicative and basic fields of research, thanks to its outstanding properties of adsorption and catalysis but also because it is a reference material for the study of many general properties of MOFs. Its metallic group comprises a pair of Cu2+ ions chelated by four carboxylate bridges, forming a structure known as paddle-wheel unit, which is the heart of the material. However, previous studies have well established that the paddle-wheel is incline to hydrolysis. In fact, the prolonged exposure of the material to moisture promotes the hydrolysis of Cu-O bonds in the paddle-wheels, so breaking the crystalline n…
Synchrotron x-ray transmission measurements and modeling of filters investigated for Athena
International audience; Advanced Telescope for High-Energy Astrophysics is a large-class astrophysics space mission selected by the European Space Agency to study the theme "Hot and Energetic Universe." The mission essentially consists of a large effective area x-ray telescope and two detectors: the X-ray Integral Field Unit (X-IFU) and the Wide Field Imager (WFI). Both instruments require filters to shield from out-of-band radiation while providing high transparency to x-rays. The mission is presently in phase B; thus, to consolidate the preliminary design, investigated filter materials need to be properly characterized by experimental test campaigns. We report results from high-resolution…
Filters design and characterization for LAD instrument onboard eXTP
Copyright 2022 Society of Photo‑Optical Instrumentation Engineers (SPIE). One print or electronic copy may be made for personal use only. Systematic reproduction and distribution, duplication of any material in this publication for a fee or for commercial purposes, and modification of the contents of the publication are prohibited. The LAD (Large Area Detector) instrument, onboard the Sino-European mission eXTP (enhanced X-ray Timing and Polarimetry), will perform single-photon, high-resolution timing and energy measurements, in the energy range 2–30 keV, with a large collecting area. Its silicon drift detectors need shielding from NIR/Vis/UV light by astrophysical sources and the bright Ea…
Investigation by raman spectroscopy of the decomposition process of HKUST-1 upon exposure to air
We report an experimental investigation by Raman spectroscopy of the decomposition process of Metal-Organic Framework (MOF) HKUST-1 upon exposure to air moisture (T=300 K, 70% relative humidity). The data collected here are compared with the indications obtained from a model of the process of decomposition of this material proposed in literature. In agreement with that model, the reported Raman measurements indicate that for exposure times longer than 20 days relevant irreversible processes take place, which are related to the occurrence of the hydrolysis of Cu-O bonds. These processes induce small but detectable variations of the peak positions and intensities of the main Raman bands of th…
The Large Area Detector onboard the eXTP mission
The Large Area Detector (LAD) is the high-throughput, spectral-timing instrument onboard the eXTP mission, a flagship mission of the Chinese Academy of Sciences and the China National Space Administration, with a large European participation coordinated by Italy and Spain. The eXTP mission is currently performing its phase B study, with a target launch at the end-2027. The eXTP scientific payload includes four instruments (SFA, PFA, LAD and WFM) offering unprecedented simultaneous wide-band X-ray timing and polarimetry sensitivity. The LAD instrument is based on the design originally proposed for the LOFT mission. It envisages a deployed 3.2 m2 effective area in the 2-30 keV energy range, a…
Carbon nanotubes thin filters for x-ray detectors in space
In this paper, we present the first results from an investigation performed on nanometric thin pellicles based on carbon nanotubes (CNT) of potential interest for manufacturing large area optical blocking filters to protect soft X-ray detectors in astrophysics space missions. In order to evaluate the effective capability of such materials to block UV/VIS/IR radiation, while being highly transparent in the soft X-rays and strong enough to withstand the severe launch stresses, we have performed a suite of characterization measurements. These include: UV/VIS/IR and X-ray absorption spectroscopy, X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy on bare and Al coated small self-…
Unveiled the Source of the Structural Instability of HKUST-1 Powders upon Mechanical Compaction: Definition of a Fully Preserving Tableting Method
Metal–organic frameworks (MOFs) are getting closer to finally being used in commercial applications. In order to maximize their packing density, mechanical strength, stability in reactive environme...
Multitechnique Analysis of the Hydration in Three Different Copper Paddle-Wheel Metal-Organic Frameworks
The structural instability in a humid environment of the majority of metal-organic frameworks (MOFs) is a challenging obstacle for their industrial-scale development. Recently, two water-resistant MOFs have been synthetized, STAM-1 and STAM-17-OEt. They both contain copper paddle wheels, like the well-known water-sensitive HKUST-1, but different organic linkers. The crystal lattice of both the MOFs undergoes a phase transition upon interaction with water molecules. Their unusual flexibility allows the controlled breaking of some interpaddle wheel Cu-O interactions in the so-called crumple zones, with a mechanism called hemilability, which is considered to have a crucial role for the stabili…
Photoluminescence properties of S2 molecule trapped in Melanophlogite
We studied the photoluminescence properties of a sample of SiO2-clathrate Melanophlogite, a crystalline microporous material which is found in nature as a rare mineral. Upon β irradiation, the material displays an intense light emission under near-UV illumination. We studied in detail this optical activity by steady-state and time-resolved photoluminescence measurements as a function of temperature. The spectroscopic properties we find can be ascribed to a population of quasi-free molecules trapped within each of the two different types of cage available in the structure of this clathrate, although the spectroscopic properties of the guest molecules are affected by their interactions with t…
Light-Induced Formation of Pb3+Paramagnetic Species in Lead Halide Perovskites
Hybrid halide perovskites are soft materials processed at room temperature, revolutionary players in the photovoltaic field. Nowadays, investigation of the nature and role of defects is seen as one of the key challenges toward full comprehension of their behavior and achievement of high device stability under working conditions. We reveal the reversible generation, under illumination, of paramagnetic Pb3+ defects in CH3NH3PbI3, synthesized in ambient conditions, induced by the presence of Pb-O defects in the perovskite structure that may trap photogenerated holes, possibly mediated by the concomitant oxidation and migration of ions. According to the mechanism that we hypothesize, one charge…
Determination of Geometry Arrangement of Copper Ions in HKUST-1 by XAFS During a Prolonged Exposure to Air
We present an experimental investigation focused on the local structural changes taking place around Cu2+ions in metalâ organic framework (MOF) HKUST-1 for different times of exposure to air by XAFS (X-ray absorption fine structure). The analysis involves both XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) regions around the Cu K-edge. Starting from the paddle-wheel structures proposed in literature, a more detailed description of the geometrical environment of Cu2+ions has been found. In particular, the paddle-wheel structure of a fresh sample, which means a pristine HKUST-1 material with a single water molecule weakly adsorbed on each C…
Radio frequency shielding of thin aluminized plastic filters investigated for the ATHENA X-IFU detector
Copyright 2018 Society of Photo-Optical Instrumentation Engineers (SPIE). One print or electronic copy may be made for personal use only. Systematic reproduction and distribution, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper are prohibited. The X-ray Integral Field Unit (X-IFU) is one of the two detectors of the ATHENA astrophysics space mission approved by ESA in the Cosmic Vision 2015-2025 Science Programme. The X-IFU consists of a large array of transition edge sensors (TES) micro-calorimeters covering a field of view of 5' diameter, sensitive in the energy range 0.2-12 keV, and providing a spectral resolution…
Confined crystallization of a HKUST-1 metal–organic framework within mesostructured silica with enhanced structural resistance towards water
A HKUST-1 metal–organic framework was crystallized in the NH2-modified mesostructured silica FDU-12 in order to improve its structural stability upon water exposure. In-depth structural characterization studies of the designed composite confirmed successful formation of the MOF phase within the ordered spherical mesopores of the silica matrix. In spite of the confinement within the cavities, MOF exhibits full accessibility for the adsorbed gas molecules. In contrast to the bulk HKUST-1, which undergoes slow phase transition in a humid environment, the structural integrity of the HKUST-1 in the humid-protective matrix remains unchanged even after immersion and stirring in water at elevated t…
Electroplated bismuth absorbers for planar NTD-Ge sensor arrays applied to hard x-ray detection in astrophysics
Single sensors or small arrays of manually assembled neutron transmutation doped germanium (NTD-Ge) based microcalorimeters have been widely used as high energy-resolution detectors from infrared to hard X-rays. Several planar technological processes were developed in the last years aimed at the fabrication of NTD-Ge arrays, specifically designed to produce soft X-ray detectors. One of these processes consists in the fabrication of the absorbers. In order to absorb efficiently hard X-ray photons, the absorber has to be properly designed and a suitable material has to be employed. Bismuth offers interesting properties in terms of absorbing capability, of low heat capacity (needed to obtain h…
The Athena X-ray Integral Field Unit: a consolidated design for the system requirement review of the preliminary definition phase
The Athena X-ray Integral Unit (X-IFU) is the high resolution X-ray spectrometer, studied since 2015 for flying in the mid-30s on the Athena space X-ray Observatory, a versatile observatory designed to address the Hot and Energetic Universe science theme, selected in November 2013 by the Survey Science Committee. Based on a large format array of Transition Edge Sensors (TES), it aims to provide spatially resolved X-ray spectroscopy, with a spectral resolution of 2.5 eV (up to 7 keV) over an hexagonal field of view of 5 arc minutes (equivalent diameter). The X-IFU entered its System Requirement Review (SRR) in June 2022, at about the same time when ESA called for an overall X-IFU redesign (i…