0000000000297711
AUTHOR
Piercarlo Mustarelli
PBI-based composite membranes for polymer fuel cells
Abstract In the present study poly(2,2-(2,6-pyridin)-5,5-bibenzimidazole) was used for the preparation of novel MEAs for high-temperature polymer fuel cells (HT-PEMFCs). We prepared hybrid materials with two types of silica fillers in order to increase the MEA performances using this polymer. The membranes were characterized in terms of their microstructure and thermal stability. Cell operation tests and Electrochemical Impedance Spectroscopy were used for the characterization of the MEAs. A maximum power density of about 80 mW cm−2 was obtained at 300 mA cm−2 by using an imidazole-modified silica filler. The EIS technique showed that the fillers chiefly help to reduce the charge transfer r…
Covalent and Ionic Functionalization of HLN Layered Perovskite by Sonochemical Methods
We describe the functionalization of the layered perovskite HLaNb2O7 with n-propanol, n-decanol, 3-mercaptopropyl-trimethoxysilane, imidazole, n-decylamine, and histamine. The use of sonication is found to significantly improve the reaction yield and to reduce the reaction time, compared to conventional thermal treatment under reflux. The obtained intercalates are thoroughly characterized through the use of several complementary experimental techniques (scanning electron microscopy, IR spectroscopy, X-ray diffraction, thermogravimetric analysis, magic-angle spinning NMR), clarifying their structure and chemical bonding. The implications for the design of inorganic–organic composite material…
Lithium ion conducting PVdF-HFP composite gel electrolytes based on N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide ionic liquid
Blends of PVDF-HFP and ionic liquids (ILs) are interesting for application as electrolytes in plastic Li batteries. They combine the advantages of the gel polymer electrolytes (GPEs) swollen by conventional organic liquid electrolytes with the nonflammability, and high thermal and electrochemical stability of ILs. In this work we prepare and characterize PVDF-HFP composite membranes swollen with a solution of LiTFSI in ether-functionalized pyrrolidinium-imide (PYRA12O1). The membranes are filled in with two different types of silica: i) mesoporous SiO2 (SBA-15) and a commercial nano-size one (HiSilTM T700). The ionic conductivity and the electrochemical properties of the gel electrolytes ar…
Optical absorption induced by UV laser radiation in Ge-doped amorphous silica probed by in situ spectroscopy
We studied the optical absorption induced by 4.7eV pulsed laser radiation on Ge-doped a-SiO2 synthesized by a sol-gel technique. The absorption spectra in the ultraviolet spectral range were measured during and after the end of irradiation with an in situ technique, evidencing the growth of an absorption signal whose profile is characterized by two main peaks near 4.5eV and 5.7eV and whose shape depends on time. Electron spin resonance measurements performed ex situ a few hours after the end of exposure permit to complete the information acquired by optical absorption by detection of the paramagnetic Ge(1) and Ge-E' centers laser-induced in the samples.
Luminescence and absorption spectroscopy of Sn-related impurity centers in silica
We report an experimental study on the absorption and luminescence spectra of oxygen deficient point defects in Sn-doped silica. The absorption band at 4.9 eV (B2β band) and the two related photoluminescence bands at ∼4.2 eV (singlet-singlet emission, S1 → S0) and at ∼3.2 eV (triplet-singlet emission, T1 → S0), linked by a thermally activated T1 → S1 inter-system crossing process (ISC), are studied as a function of temperature from 300 to 20 K. This approach allows us to investigate the dynamics properties of the matrix in the surroundings of the point defects and the effects of local disorder on the two relaxation processes from S1: the radiative channel to S0 and the ISC process to T1. We…
MCM-41 silica effect on gel polymer electrolytes based on thermoplastic polyurethane
Abstract Polymer electrolytes were prepared from thermoplastic polyurethane with addition of mixture of N-ethyl(methylether)-N-methylpyrrolidinium trifluoromethanesulfonimide (PYRA12O1TFSI) ionic liquid, lithium bis(trifluoromethanesulfoneimide) salt and propylene carbonate. MCM-41 mesoporous silica was added in proportions ranging from 5 to 20 wt.% with respect to TPU. The electrolytes were characterized by thermogravimetric analysis, differential scanning calorimetry, linear voltammetry and impedance spectroscopy. The MCM-41 addition to the system was found to improve the electrochemical stability of the membranes and to reduce the gel electrolyte/metallic Li interfacial resistance. The f…
Synthesis and Characterisation of Functionalized borosilicate nanoparticles for boron neutron capture therapy applications
Boron Neutron Capture Therapy (BNCT) is a promising therapy for the cure of diffuse tumors. The successful clinical application of BNCT requires finding new boron-based compounds suitable for an efficient 10B delivery to the cancerous tissues. The purpose of this work is to synthesize borosilicate nanoparticles by a sol–gel recipe, and to functionalize them with folic acid in order to promote their capture by the tumor cells. Whereas sol–gel is a promising technique for the synthesis of nanoparticles, in case of borosilicate systems this approach is affected by significant boron loss during preparation. Here we show that functionalization of borosilicate nanoparticles with folic acid can re…
S29i attribution of the 1.3 mT hyperfine structure of the E′γ centers in amorphous SiO2
We report an experimental investigation by electron paramagnetic resonance of the doublet of lines split by ∼1.3 mT and centered on the E′γ; center resonance line in the spectrum of irradiated amorphous SiO2 . Commercial and sol-gel materials, some of which subjected to hydrogen-deuterium exchange, were investigated. Exposure to γ or Β rays at room temperature of the samples and subsequent thermal treatments were carried out to induce the defects and to study their thermal stability. In all the materials used the ratio between the signal of the E′γ centers and that of the 1.3 mT doublet is constant and independent of the OH and OD contents. Furthermore, the 1.3 mT doublet and the E′γ center…
Average versus local structure in K2NiF4-type LaSrAlO4: direct experimental evidence of local cationic ordering
The long-range ordering of a crystalline material can be accurately determined by analyzing the Bragg intensities and positions. In contrast, direct observation of short-range ordering in crystalline materials, which is increasingly considered of fundamental importance to unravel the structure-property relationships that underpin their technological applications, is a challenging task. In this study we have investigated the structure of LaSrAlO4, a representative example of compounds with the K2NiF4-type structure. By the combined use of synchrotron and neutron diffraction, pair distribution function analysis, Al-27 MQMAS NMR and atomistic simulations we have highlighted differences between…
Solid-state NMR characterization of the structure and thermal stability of hybrid organic-inorganic compounds based on a HLaNb2O7 Dion-Jacobson layered perovskite.
Dion-Jacobson phases, like MLaNb2O7, are an interesting class of ion-exchangeable layered perovskites possessing electronic and photocatalytic properties. Their protonated and organo-modified homologues, in particular, have already been indicated as promising catalysts. However, the structural analysis of these highly tailorable materials is still incomplete, and both the intercalation process and thermal stability of the included organic moieties are far from being completely understood. In this study, we present a thorough solid-state NMR characterization of HLaNb2O7·xH2O intercalated with different amounts of octylamine, or with decylamine. Samples were analyzed as prepared, and after th…