Synthesis of azole biophospanates presursors for proton-exchange membrane for application in high temperature PEM fuel cells

This work reports the synthesis and characterization of phosphonate-, hydroxybisphosphonate- and aminobisphosphonatebenzimidazole derivatives substituted at N-1 position and new regioisomers phosphonateand aminobisphosphonatebenzotriazole derivatives substituted at N-1 or N-2 positions. The compounds were characterized by NMR, IR spectroscopy and mass spectrometry (low and high resolution) allowing the assignment of their structure, including the identification of regioisomers. These azoles will be precursors of mesoporous silica host to produce novel membranes materials with high proton conductivity for intermediate temperature PEMFCs

Synthesis and characterization of new azaheterocyclic aromatic phosphonates for hybrid materials for fuel cell applications

ABSTRACT: This work reports the synthesis and characterization of new azaheterocyclic aromatic phosphonates derivated from benzimidazole and benzotriazole by nickel-catalyzed Arbuzov reaction of 4,7-dibromo-2,1,3-benzothiadiazole with triethyl phosphite, followed by reductive sulfur extrusion reaction and cyclization. The compounds were characterized by NMR and mass spectrometry (low and high resolution). These azoles will be incorporated into proton conductive inorganic-organic hybrid membranes of mesoporous silica to produce novel membranes materials with high proton conductivity for intermediate temperature PEMFCs.info:eu-repo/semantics/publishedVersio

Synthesis of new azole phosphonate precursors for fuel cells proton exchange membranes

Herein we present the synthesis and characterization of new phosphonate-, bisphosphonate- and hydroxybisphosphonatebenzimidazole derivatives substituted at the N-1 position and new regioisomers phosphonate-, bisphosphonate-, and hydroxybisphosphonatebenzotriazole derivatives substituted at N-1 or N-2 positions. The compounds were characterized by NMR and IR spectroscopies, and mass spectrometry (low and high resolution) allowing the assignment of their structure, including the identification of regioisomers. These new azole monomers will be precursors for a mesoporous silica host to produce novel membrane materials with high proton conductivity for intermediate temperature proton exchange membrane fuel cells

New proton conductive membranes of indazole- and condensed pyrazolebisphosphonic acid-Nafion membranes for PEMFC

ABSTRACT: The global demands of energy are still increasing alongside many civilizational problems, notably the effects on the environment due to the overuse of traditional energy sources based on fossil fuels. New cleaner, renewable sources for sustainable energy systems are a key challenge of the 21st century society.N/

New proton conductive membranes of indazole- and condensed pyrazolebisphosphonic acid-Nafion membranes for PEMFC

ABSTRACT: In this work, new doped Nafion membranes for PEMFC are prepared by casting with 1 wt% loading of the prepared indazole- and condensed pyrazolebisphosphonic acids (AzBPs). The new membranes were analysed by ATR-FTIR spectroscopy and their morphology was examined by SEM. Membranes were evaluated for water uptake and ion exchange capacity (IEC), and their hydration number was estimated. The proton conduction properties of the modified membranes were evaluated by electrochemical impedance spectroscopy (EIS), at different temperatures (30, 40, 50 and 60 °C) and relative humidity (RH) (40, 60 and 80%). The proton conductivities of all membranes increase with increasing temperature and RH. Also, all new membranes doped with AzBPs exhibited higher proton conductivities than Nafion N-115, used as a reference and tested at the same experimental conditions, with values up to 1.5-fold. Results show that the incorporation of AzBPs dopants on Nafion membranes enhances the proton conduction throughout the modified membranes. The best proton conductivity was observed for membranes with AzBP1 as dopant, with a value of 94 mS cm-1. These results indicate that the Nafion membranes doped with indazole- and condensed pyrazolebisphosphonic acids are a promising approach for new membranes for PEMFC with improved proton conductivity.info:eu-repo/semantics/publishedVersio

Chemical stability of new nafion membranes doped with bisphosphonic acids under Fenton oxidative conditions

ABSTRACT: The development of new proton exchange membranes for PEM technology in fuel cells and electrolysers with increased durability is paramount to system's lifetime and scalability. In this work, new modified Nafion membranes doped with bisphosphonic acids are proposed with increased resilience to chemical degradation by H2O2/Fe2+, mimicking ex-situ radical attack to membrane structure. Relevant properties were evaluated throughout Fenton's test using fluoride ion release and gravimetry determinations, and by ATR-FTIR spectros-copy and SEM before and after the chemical degradation. The new membranes showed a very good chemical stability after oxidative degradation under Fenton's test conditions at 80 degrees C, with more durability than Nafion 115 commercial membrane. After chemical degradation, the proton conduction of the membranes was assessed through EIS which reveals a decrease in the proton conductivity of all membranes, with the new modified membranes showing a smaller decrease of their proton conduction properties than Nafion 115 membrane. Fluoride ion release, weight loss measurements and ATR-FTIR spectros-copy data analysis suggest degradation of the side chain of the ionomer.info:eu-repo/semantics/publishedVersio

Infrared spectroscopic studies of novel hydroxybisphosphonates and molecular modelling of their interaction with hydroxyapatite

Bisphosphonates (BPs) are a class of drugs widely used in the treatment of several metabolic bone disorders associated with increased bone resorption, including osteoporosis, Paget’s disease and metastic bone disease [1]. Although BPs can directly inhibit the cellular activity of osteoclasts, their ability to adsorb to bone mineral is also an important factor in determining their potency and duration of action [2]. In this study, we performed a molecular modelling analysis, by molecular mechanics, of the molecular structures of hydroxy(1H-indazol-3-yl)methylenediphosphonic acid (BP1; Figure 1a) and hydroxy(1-methyl-1H-indazol-3-yl)methylenediphosphonic acid (BP2; Figure 1b) and examined their interactions with hydroxyapatite (HA) by energy-minimising 50 different orientations for judiciously selected low energy conformers of each ligand at 10 Å from the mineral surface. We also calculated the vibrational spectra for each BP with semiempirical methods and compared then with FTIR spectra obtained experimentaly. The calculated interaction energies of the studied BPs with HA suggests that BP2 interacts stronger with hydroxyapatite than BP1. These results are in agreement with in vitro and in vivo studies of the 153Sm-BPs complexes. Complex 153Sm-BP2 showed, in vitro, higher HA binding than complex 153Sm-BP1. In vivo studies showed different farmacokinetics parameters with complex 153Sm-BP2 presenting initial higher levels of bone uptake than complex 153Sm-BP1, which concentration is increasing during the 24 h period studied

New Approach for Temporal Stability Evaluation of Pseudo-Invariant Calibration Sites (PICS)

Pseudo-Invariant Calibration Sites (PICS) are one of the most popular methods for in-flight vicarious radiometric calibration of Earth remote sensing satellites. The fundamental question of PICS temporal stability has not been adequately addressed. However, the main purpose of this work is to evaluate the temporal stability of a few PICS using a new approach. The analysis was performed over six PICS (Libya 1, Libya 4, Niger 1, Niger 2, Egypt 1 and Sudan 1). The concept of a Virtual Constellation was developed to provide greater temporal coverage and also to overcome the dependence limitation of any specific characteristic derived from one particular sensor. TOA reflectance data from four sensors consistently demonstrating stable calibration to within 5%the Landsat 7 ETM+ (Enhanced Thematic Mapper Plus), Landsat 8 OLI (Operational Land Imager), Terra MODIS (Moderate Resolution Imaging Spectroradiometer) and Sentinel-2A MSI (Multispectral Instrument)were merged into a seamless dataset. Instead of using the traditional method of trend analysis (Students T test), a nonparametric Seasonal Mann-Kendall test was used for determining the PICS stability. The analysis results indicate that Libya 4 and Egypt 1 do not exhibit any monotonic trend in six reflective solar bands common to all of the studied sensors, indicating temporal stability. A decreasing monotonic trend was statistically detected in all bands, except SWIR 2, for Sudan 1 and the Green and Red bands for Niger 1. An increasing trend was detected in the Blue band for Niger 2 and the NIR band for Libya 1. These results do not suggest abandoning PICS as a viable calibration source. Rather, they indicate that PICS temporal stability cannot be assumed and should be regularly monitored as part of the sensor calibration process