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The effect of semiconducting tungsten disulfide (WS2) nanoparticles (NPs), functionalized by either methacryloxy, glycidyl, vinyl, or amino silanes, has been studied in photocuring of acrylate and epoxy resins (the latter photocured according to a cationic mechanism). The curing time, degree of curing (DC), thermal effects, and mechanical properties of the radiation-cured resins were investigated. X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses confirmed that a silane coating was formed (1–4 nm) on the NPs' surface having a thickness of 1–4 nm. Fourier transition infrared (FTIR) was used to determine the DC of the nanocomposite resin. The curing time of the epoxy resin, at 345–385 nm wavelength, was 10 to 20 s, while for acrylate, the curing time was 7.5 min, reaching 92% DC in epoxy and 84% in acrylate. The glass transition temperature (Tg) of the photocured acrylates in the presence of WS2 NPs increased. In contrast to the acrylate, the epoxy displayed no significant variations of the Tg. It was found that the silane surface treatments enhanced the DC. Significant increases in impact resistance and enhancement in shear adhesion strength were observed when the NPs were treated with vinyl silane. A previous study has shown that the addition of WS2 NPs at a concentration of 0.5 wt.% is the optimal loading for improving the resin's mechanical properties. This study supports these earlier findings not only for the unmodified NPs but also for those functionalized with silane moieties. This study opens new vistas for the photocuring of resins and polymers in general when incorporating WS2 NPs. [ABSTRACT FROM AUTHOR]

Herein we present a series of new α-iminopyridine-based iron-PNN pincer complexes [FeBr2LPNN] (1), [Fe(CO)2LPNN] (2), [Fe(CO)2LPNN](BF4) (3), [Fe(F)(CO)2LPNN](BF4) (4), and [Fe(H)(CO)2LPNN](BF4) (5) with formal oxidation states ranging from Fe(0) to Fe(II) (LPNN = 2-[(di-tert-butylphosphino)methyl]-6-[1-(2,4,6-mesitylimino)ethyl]pyridine). The complexes were characterized by a variety of methods including ¹H, 13C, 15N, and 31P NMR, IR, Mössbauer, and X-ray photoelectron spectroscopy (XPS) as well as electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopy, SQUID magnetometry, and X-ray crystallography, focusing on the assignment of the metal oxidation states. Ligand structural features suggest that the α-iminopyridine ligand behaves as a redox non-innocent ligand in some of these complexes, particularly in [Fe(CO)2LPNN] (2), in which it appears to adopt the monoanionic form. In addition, the NMR spectroscopic features (13C, 15N) indicate the accumulation of charge density on parts of the ligand for 2. However, a combination of spectroscopic measurements that more directly probe the iron oxidation state (e.g., XPS), density functional theory (DFT) calculations, and electronic absorption studies combined with time-dependent DFT calculations support the description of the metal atom in 2 as Fe(0). We conclude from our studies that ligand structural features, while useful in many assignments of ligand redox non-innocence, may not always accurately reflect the ligand charge state and, hence, the metal oxidation state. For complex 2, the ligand structural changes are interpreted in terms of strong back-donation from the metal center to the ligand as opposed to electron transfer. [ABSTRACT FROM AUTHOR]

Abstract: Structural changes in multi-walled carbon nanotubes (CNTs) resulting from covalent functionalization during oxidation were studied by transmission electron microscopy, X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Strong correlation is found between the oxidation progress (i.e. increase in the amount of oxygen and oxidized carbon) and the degradation in inter-atomic conjugation, the latter being inferred from the intensity of satellite (‘shake-up’) lines in the C1s XPS spectrum. Moreover, defects appear to cluster rather than distribute at random along the CNTs. Hints on the sites most vulnerable to the progress of the chemical attack are provided. Defect clustering leads as well to deterioration of inner layers of nanotubes at relatively early stages of the chemical attack. As a consequence, the mechanical strength of the CNTs degrades but the resultant interface with a host matrix can become physically intermittent, which may positively contribute to the composite strength and toughness. [Copyright &y& Elsevier]

Abstract: The presence of water at the surface of sputtered thin films of Ce0.8Gd0.2O1.9, which display elastic anomalies as a function of thermal treatment, and of stoichiometric CeO2 films, which do not, was monitored using X-ray photoelectron spectroscopy. We find that considerably more water is strongly bound at the surface of the Ce0.8Gd0.2O1.9 films than of the CeO2 films. This supports the theoretical prediction that water binds preferentially at the oxygen vacancy sites. In addition, all films were treated according to the protocol which has been shown to produce inelastic behavior in the doped films: annealed at 500°C, exposed to ambient atmosphere for one month and then heated to 250°C in ultra-high vacuum. Neither the Ce0.8Gd0.2O1.9 nor the CeO2 films show any change in the amount of adsorbed water. We therefore conclude that changes in the amount of surface adsorbed water do not play a role in the elastic anomalies observed as a function of thermal treatment of Ce0.8Gd0.2O1.9 films. [Copyright &y& Elsevier]

Surface degradation is a major limitation in the utilization of high energy cathodes. Cathode coatings provide a promising route for achieving interfacial stability. In this case, there is interest in developing coatings which will provide efficient ion transport across the cathode-electrolyte-interface (CEI). Aluminum based coatings, particularly metal fluorides, have shown great promise for stabilizing the high voltage cathode, LiNi 0.5 Mn 1.5 O 4. Despite the clear practical advantages of coatings, the chemical basis for their improved performance remains ambiguous. Here we present an in-depth investigation of a nominal AlF 3 coating on LiNi 0.5 Mn 1.5 O 4 based on solid state NMR spectroscopy to determine the composition and function of the Al/F coating layer. NMR results, supported by X-ray photoelectron spectroscopy and electron microscopy, reveal that the actual composition of the deposited layer is an amorphous Al–O–F phase. Isotope exchange is used to follow the spontaneous exchange of lithium ions across the CEI, revealing improved transport in coated cathodes. Finally, NMR experiments provide evidence for insertion of lithium ions in the Al/F coating following electrochemical cycling. The results suggest that lithium insertion into a nominally lithium-less coating plays a role in its improved performance, highlighting lithium content as an important factor in designing beneficial coatings for higher energy cathodes. [Display omitted] • We studied the origin of improved cathode performance with a lithium-less coating. • We determined the composition of a thin coating for cathodes using XPS and ss NMR. • NMR showed faster ion exchange across coated cathodes. • Partial coating lithiation with cycling is identified and may improve transport. [ABSTRACT FROM AUTHOR]