Composite hypo-hyper-d-intermetallic and interionic phases as supported interactive electrocatalysts

Interactive, strong interbonding and highly electron conductive nonstoichiometric titanium suboxide catalytic supports, Magneli phases (Ti(n)O(2n-1), on average Ti(4)O(7)), have been used in the electrocatalysis of hydrogen (HELR) and oxygen (OELR) electrode reactions with remarkable consequences and advanced achievements. The theory of hypo-hyper-d-interelectronic bonding of transition metal ions and atoms has been employed for selective ordered grafting and shown to stay in the core of the strong metal-support interaction (SMSI) in heterogeneous catalysis and electrocatalysis, and thereby the substantial cause for the improved synergistic activity of composite (electro)catalysts. The same fundament has been the thermodynamic basis for the thermal production of symmetric intermetallic Laves type phases of nanostructured electrocatalysts, in particular the ones with higher oxophilic properties of hypo-d-elements. Remarkably advanced in electrocatalytic activity, highly monatomically dispersed deposits of Pt upon Magneli phases are shown to be unique and highly promising electrocatalysts for the cathodic oxygen reduction (ORR). Nanostructured Au upon a thin nanocrystalline film of anatase titania has been confirmed by X-ray photoelectron spectroscopy (XPS) as a typical classical paradigm of the SMSI, and at the same time affording the basis for gold with strained d-orbitals, as the reversible hydrogen electrode. Magneli phases have been shown to be the best electrocatalytic supports with unique properties both for low temperature PEM fuel cells (LT PEM FCs) with pronounced CO tolerance and water electrolysis in membrane type hydrogen generators.     

Thermal stability study of nitrogen functionalities in a graphene network

Catalyst-free vertically aligned graphene nanoflakes possessing a large amount of high density edge planes were functionalized using nitrogen species in a low energy N(+) ion bombardment process to achieve pyridinic, cyanide and nitrogen substitution in hexagonal graphitic coordinated units. The evolution of the electronic structure of the functionalized graphene nanoflakes over the temperature range 20-800?°C was investigated in situ, using high resolution x-ray photoemission spectroscopy. We demonstrate that low energy irradiation is a useful tool for achieving nitrogen doping levels up to 9.6 at.%. Pyridinic configurations are found to be predominant at room temperature, while at 800?°C graphitic nitrogen configurations become the dominant ones. The findings have helped to provide an understanding of the thermal stability of nitrogen functionalities in graphene, and offer prospects for controllable tuning of nitrogen doping in device applications.     

Aqueous-phase exfoliation of graphite in the presence of polyvinylpyrrolidone for the production of water-soluble graphenes

Treatment of crystalline graphite fine powder with an aqueous solution of the harmless and versatile substance polyvinylpyrrolidone under sonication results in water-soluble, polymer-protected graphene single layers without oxidation or destruction of the sp² character of the carbon core. The liquid-phase extraction of graphene monolayers was evidenced by TEM and AFM techniques, while their graphitic character was checked with Raman spectroscopy. Besides PVP, the water-soluble biopolymers albumin and sodic carboxymethylcellulose were also employed successfully in the aqueous-phase exfoliation of graphite, thereby supporting the generic character of the present method using a variety of suitable polymeric extractants.     

Microdeposition of metal and oxide structures using ultrashort laser pulses

2 O₃ on glass and silicon substrates is performed. The superior quality of the results allows the direct, one-step fabrication of binary-amplitude and multilevel optical diffractive structures. Received: 4 February 1998/Accepted: 9 February 1998     

5-dimensional braneworld with gravitating Nambu–Goto matching conditions

We continue the investigation of a recent proposal on alternative matching conditions for self-gravitating defects which generalize the standard matching conditions. The reasoning for this study is the need for consistency of the various codimension defects and the existence of a meaningful equation of motion at the probe limit, things that seem to lack from the standard approach. These matching conditions arise by varying the brane–bulk action with respect to the brane embedding fields (and not with respect to the bulk metric at the brane position) in a way that takes into account the gravitational back-reaction of the brane to the bulk. They always possess a Nambu–Goto probe limit and any codimension defect is seemingly consistent for any second order bulk gravity theory. Here, we consider in detail the case of a codimension-1 brane in five-dimensional Einstein gravity, derive the generic alternative junction conditions and find the Z₂$Z_2$-symmetric braneworld cosmology, as well as its bulk extension. Compared to the standard braneworld cosmology, the new one has an extra integration constant which accounts for the today matter and dark energy contents, therefore, there is more freedom for accommodating the observed cosmic features. One branch of the solution possesses the asymptotic linearized LFRW regime. We have constrained the parameters so that to have a recent passage from a long deceleration era to a small today acceleration epoch and we have computed the age of the universe, consistent with current data, and the time-varying dark energy equation of state. For a range of the parameters it is possible for the presented cosmology to provide a large acceleration in the high energy regime.     

Determination of residues of UV filters in natural waters by solid-phase extraction coupled to liquid chromatography-photodiode array detection and gas chromatography-mass spectrometry

This study describes a procedure for the enrichment, separation and quantification of four major UV filters in natural waters. Solid-phase extraction combined with liquid chromatography and photodiode array detection (LC-UV-DAD), and gas chromatography with mass spectroscopy (GC-MS) were employed for the analyses. LC of the four compounds with surfactant-modified hydro-organic eluents gave satisfactory resolution of overlapping peaks. In GC, a significant improvement of the detection limits was attained, but only three compounds could be detected. The method was validated for, and applied to, various water samples prone to UV filter accumulation due to recreational activities. Recoveries from real samples were 86-99% with LOQs as low as 0.5 ng/l depending on the sample volume and the analytical procedure.     

Cyclic voltammetry and bulk electronic properties of soluble carbon nanotubes

The bulk electronic properties of pyrrolidine-functionalized nanotubes are obtained from cyclic voltammetry measurements and discussed in the light of quantum chemical calculations. The functionalization is found to preserve the metallic character and to hardly affect the average density of electronic states.     

An analytical method for the simultaneous trace determination of acidic pharmaceuticals and phenolic endocrine disrupting chemicals in wastewater and sewage sludge by gas chromatography-mass spectrometry

This article presents an analytical method based on solid-phase extraction (SPE) and gas chromatography coupled with mass spectrometry for the simultaneous determination of the most frequently used acidic pharmaceutical residues, ibuprofen, diclofenac, naproxen and ketoprofen (KFN), and phenolic endocrine disruptors, bisphenol (BPA), triclosan (TCS), nonylphenol, nonylphenol monoethoxylate and nonylphenol diethoxylate, in wastewater and sewage sludge samples. In the first phase of the study, each compound has been characterized individually and afterwards in mixture as a trimethylsilyl derivative in order to identify the characteristic ions (m/z ratio) constituting the mass spectrum and to choose the ions for quantification and confirmation. Subsequently, derivatization was evaluated by testing different variables such as the volume of the derivatization solvent bis(trimethylsilyl)trifluoroacetamide and the effect of each catalyst, pyridine and 1% trimethyl chlorosilane, in the derivatized solution. For the analysis of wastewater samples, two commercial SPE cartridges, C18 and Oasis HLB, were compared for their extraction efficiency of the target compounds. The key parameter of extraction procedure included the effect of pH (2.5, 5.3 and 7) of the loading solution. For solid samples, parameters such as the extracted biomass, the volume of the extraction organic solvent and the effect of matrix interferences in chromatographic analysis were evaluated. By using C18 cartridges as purification procedure and ultrasound sonication, satisfactory mean relative recoveries with BPA-d16 and meclofenamic acid as surrogates were obtained ranging from 91% to 117% for wastewater and 84% to 107% for sewage sludge samples. Nine-point calibration of the standard mixture was performed by linear regression analysis with a correlation coefficient >0.99 for all the tested compounds. Limits of detection for the developed methods were established between 0.3 (KFN) and 14.8 (BPA) ng L⁻¹, and 15.0 (TCS) and 32.9 (BPA) ng g⁻¹ for wastewater and sewage sludge, respectively. Application to real samples of the wastewater treatment plant in Athens, the capital of Greece, demonstrated the presence of all tested compounds in most of the samples.     

Time-resolved velocity map imaging of methyl elimination from photoexcited anisole

To date, H-atom elimination from heteroaromatic molecules following UV excitation has been extensively studied, with the focus on key biological molecules such as chromophores of DNA bases and amino acids. Extending these studies to look at elimination of other non-hydride photoproducts is essential in creating a more complete picture of the photochemistry of these biomolecules in the gas-phase. To this effect, CH(3) elimination in anisole has been studied using time-resolved velocity map imaging (TR-VMI) for the first time, providing both time and energy information on the dynamics following photoexcitation at 200 nm. The extra dimension of energy afforded by these measurements has enabled us to address the role of πσ* states in the excited state dynamics of anisole as compared to the hydride counterpart (phenol), providing strong evidence to suggest that only CH(3) fragments eliminated with high kinetic energy are due to direct dissociation involving a (1)πσ* state. These measurements also suggest that indirect mechanisms such as statistical unimolecular decay could be contributing to the dynamics at much longer times.