Target Structure Induced Suppression of the Ionization Cross Section for Very Low Energy Antiproton-Hydrogen Collisions

Low energy antiprotons have been used previously to give benchmark data for theories of atomic collisions. Here we present measurements of the cross section for single, nondissociative ionization of molecular hydrogen for impact of antiprotons with kinetic energies in the range 2-11 keV, i.e., in the velocity interval of 0.3-0.65 a.u. We find a cross section which is proportional to the projectile velocity, which is quite unlike the behavior of corresponding atomic cross sections, and which has never previously been observed experimentally.

A STUDY OF CARBON-MONOXIDE AND NEUTRAL CARBON IN THE S106 MOLECULAR CORE

Maps are presented of J=2-1 and J=3-2 (CO)-O-18 emission from the molecular environment of the bipolar nebula S106, together with complementary observations of the P-3(1)-P-3(0), C I emission. Line splitting observed extensively over the E molecular cloud suggests that it is best explained as the expanding remnant of a thick toroid surrounding the optical lobes. The poor correlation between the observed molecular line emission and dust continuum emission in the E cloud is probably due to a large temperature gradient. Strong C I emission from the protostellar candidate S106 FIR suggests the nearby presence of a powerful source of far-UV radiation, whose energy supply is unlikely to arise from gravitational contraction of a protostar. It is probable that this source is the star S106 LR, which also heats S106 FIR. There is evidence, in both C I and (CO)-O-18, for a predominantly blueshifted outflow from S106 IR, best interpreted as a stellar wind-driven shock into the toroidal remnant. (CO)-O-18 and (CO)-C-13 appear to be depleted, relative to canonical values for their abundances, in S106 FIR, despite its high optical extinction, which should discourage selective photodissociation. Elsewhere in the cloud the C I line profiles show a resemblance to those of (CO)-O-18, with intensity equivalent to a few photodissociation regions (PDRs) along the line of sight.

A density functional theory study of hydrogen dissociation and diffusion at the perimeter sites of Au/TiO2

Reactivity of supported gold catalysts is a hot topic in catalysis for many years. This communication reports an investigation on the dissociation of molecular hydrogen at the perimeter sites of Au/TiO2 and the spillover of hydrogen atoms from the gold to the support using density functional theory calculations. It is found that the heterolytic dissociation is favoured in comparison with homolytic dissociation of molecular hydrogen at the perimeter sites. However, the surface oxygen of the rutile TiO2(110) surface at these sites can be readily passivated by the formed OH, suggesting that further dissociation of molecular hydrogen may occur at pure gold sites.

Spatial analysis of C2 band emission from laser produced plasma

Time and space resolved spectroscopic studies of the molecular band emission from C2 are performed in the plasma produced by irradiating a graphite target with 1:06 m radiation from a Q-switched Nd:YAG laser. High-resolution spectra are recorded from points located at distances up to 15 mm from the target in the presence of ambient helium gas pressure. Depending on the laser irradiance, time of observation and position of the sampled volume of the plasma the features of the emission spectrum are found to change drastically. The vibrational temperature and population distribution in the different vibrational levels of C2 molecules have been evaluated as a function of distance for different time delays and laser irradiance. It is also found that the vibrational temperature of C2 molecules decreases with increasing helium pressure.

Tin and tin-titanium as catalyst components for reversible hydrogen storage of sodium aluminium hydride

This paper is concerned with the effects of adding tin and/or titanium dopant to sodium aluminium hydride for both dehydrogenation and re-hydrogenation reactions during their reversible storage of molecular hydrogen. Temperature programmed decomposition (TPD) measurements show that the dehydrogenation kinetics of NaAlH4 are significantly enhanced upon doping the material with 2 mol% of tributyltin hydride, Sn(Bu)(3)H but the tin catalyst dopant is shown to be inferior than titanium. On the other hand, in this preliminary work, a significant synergetic catalytic effect is clearly revealed in material co-doped with both titanium and tin catalysts which shows the highest reversible rates of dehydrogenation and re-hydrogenation (after their hydrogen depletion). The re-hydrogenation rates of depleted Sn/Ti/NaAlH4 evaluated at both 9.5 and 140 bars hydrogen are also found to be favourable compared to the Ti/NaAlH4, which clearly suggest the importance of the catalyst choice. Basing on these results some mechanistic insights for the catalytic reversible dehydrogenation and re-hydrogenation processes of Sn/Ti/NaAlH4 are therefore made. (C) 2006 Elsevier Ltd. All rights reserved.

Hydrogen adsorption in a copper ZSM5 zeolite: an inelastic neutron scattering study

Currently microporous oxidic materials including zeolites are attracting interest as potential hydrogen storage materials. Understanding how molecular hydrogen interacts with these materials is important in the rational development of hydrogen storage materials and is also challenging theoretically. In this paper, we present an incoherent inelastic neutron scattering (INS) study of the adsorption of molecular hydrogen and hydrogen deuteride (HD) in a copper substituted ZSM5 zeolite varying the hydrogen dosage and temperature. We have demonstrated how inelastic neutron scattering can help us understand the interaction of H-2 molecules with a binding site in a particular microporous material, Cu ZSM5, and by implication of other similar materials. The H-2 molecule is bound as a single species lying parallel with the surface. As H-2 dosing increases, lateral interactions between the adsorbed H-2 molecules become apparent. With rising temperature of measurement up to 70 K (the limit of our experiments), H-2 molecules remain bound to the surface equivalent to a liquid or solid H-2 phase. The implication is that hydrogen is bound rather strongly in Cu ZSM5. Using the simple model for the anisotropic interaction to calculate the energy levels splitting, we found that the measured rotational constant of the hydrogen molecule is reduced as a consequence of adsorption by the Cu ZSM5. From the decrease in total signal intensity with increasing temperature, we were able to observe the conversion of para-hydrogen into ortho-hydrogen at paramagnetic centres and so determine the fraction of paramagnetic sites occupied by hydrogen molecules, ca. 60%. (c) 2006 Elsevier B.V. All rights reserved.

Methane in the atmosphere of the transiting hot Neptune GJ436b?

We present an analysis of seven primary transit observations of the hot Neptune GJ436b at 3.6, 4.5, and 8 μm obtained with the Infrared Array Camera on the Spitzer Space Telescope. After correcting for systematic effects, we fitted the light curves using the Markov Chain Monte Carlo technique. Combining these new data with the EPOXI, Hubble Space Telescope, and ground-based V, I, H, and Ks published observations, the range 0.5-10 μm can be covered. Due to the low level of activity of GJ436, the effect of starspots on the combination of transits at different epochs is negligible at the accuracy of the data set. Representative climate models were calculated by using a three-dimensional, pseudospectral general circulation model with idealized thermal forcing. Simulated transit spectra of GJ436b were generated using line-by-line radiative transfer models including the opacities of the molecular species expected to be present in such a planetary atmosphere. A new, ab-initio-calculated, line list for hot ammonia has been used for the first time. The photometric data observed at multiple wavelengths can be interpreted with methane being the dominant absorption after molecular hydrogen, possibly with minor contributions from ammonia, water, and other molecules. No clear evidence of carbon monoxide and carbon dioxide is found from transit photometry. We discuss this result in the light of a recent paper where photochemical disequilibrium is hypothesized to interpret secondary transit photometric data. We show that the emission photometric data are not incompatible with the presence of abundant methane, but further spectroscopic data are desirable to confirm this scenario.

Hydrogen evolution by a metal-free electrocatalyst

Electrocatalytic reduction of water to molecular hydrogen via the hydrogen evolution reaction may provide a sustainable energy supply for the future, but its commercial application is hampered by the use of precious platinum catalysts. All alternatives to platinum thus far are based on nonprecious metals, and, to our knowledge, there is no report about a catalyst for electrocatalytic hydrogen evolution beyond metals. Here we couple graphitic-carbon nitride with nitrogen-doped graphene to produce a metal-free hybrid catalyst, which shows an unexpected hydrogen evolution reaction activity with comparable overpotential and Tafel slope to some of well-developed metallic catalysts. Experimental observations in combination with density functional theory calculations reveal that its unusual electrocatalytic properties originate from an intrinsic chemical and electronic coupling that synergistically promotes the proton adsorption and reduction kinetics.

Hydrogen production by biogas steam reforming: A technical, economic and ecological analysis

Fuel cells are electrochemical energy conversion devices that convert fuel and oxidant electrochemically into electrical energy, water and heat. Compared to traditional electricity generation technologies that use combustion processes to convert fuel into heat, and then into mechanical energy, fuel cells convert the hydrogen and oxygen chemical energy into electrical energy, without intermediate conversion processes, and with higher efficiency. In order to make the fuel cells an achievable and useful technology, it is firstly necessary to develop an economic and efficient way for hydrogen production. Molecular hydrogen is always found combined with other chemical compounds in nature, so it must be isolated. In this paper, the technical, economical and ecological aspects of hydrogen production by biogas steam reforming are presented. The economic feasibility calculation was performed to evaluate how interesting the process is by analyzing the investment, operation and maintenance costs of the biogas steam reformer and the hydrogen production cost achieved the value of 0.27 US$/kWh with a payback period of 8 years. An ecological efficiency of 94.95%, which is a good ecological value, was obtained. The results obtained by these analyses showed that this type of hydrogen production is an environmentally attractive route. © 2013 Elsevier Ltd.

New materials for electrochemiluminescence

The study of electrochemiluminescence (ECL) involves photophysical and electrochemical aspects. Excited states are populated by an electrical stimulus. The most important applications are in the diagnostic field where a number of different biologically-relevant molecules (e.g. proteins and nucleic acids) can be recognized and quantified with a sensitivity and specificity previously not reachable. As a matter of fact the electrochemistry, differently to the classic techniques as fluorescence and chemiluminescence, allows to control the excited state generation spatially and temporally. The two research visits into A. J. Bard electrochemistry laboratories were priceless. Dr. Bard has been one of ECL pioneers, the first to introduce the technique and the one who discovered in 1972 the surprising emission of Ru(bpy)3 2+. I consider necessary to thank by now my supervisors Massimo and Francesco for their help and for giving me the great opportunity to know this unique science man that made me feel enthusiastic. I will never be grateful enough… Considering that the experimental techniques of ECL did not changed significantly in these last years the most convenient research direction has been the developing of materials with new or improved properties. In Chapter I the basics concepts and mechanisms of ECL are introduced so that the successive experiments can be easily understood. In the final paragraph the scopes of the thesis are briefly described. In Chapter II by starting from ECL experimental apparatus of Dr. Bard’s laboratories the design, assembly and preliminary tests of the new Bologna instrument are carefully described. The instrument assembly required to work hard but resulted in the introduction of the new technique in our labs by allowing the continuation of the ECL studies began in Texas. In Chapter III are described the results of electrochemical and ECL studies performed on new synthesized Ru(II) complexes containing tetrazolate based ligands. ECL emission has been investigated in solution and in solid thin films. The effect of the chemical protonation of the tetrazolate ring on ECL emission has been also investigated evidencing the possibility of a catalytic effect (generation of molecular hydrogen) of one of the complexes in organic media. Finally, after a series of preliminary studies on ECL emission in acqueous buffers, the direct interaction with calf thymus DNA of some complexes has been tested by ECL and photoluminescence (PL) titration. In Chapter IV different Ir(III) complexes have been characterized electrochemically and photophysically (ECL and PL). Some complexes were already well-known in literature for their high quantum efficiency whereas the remaining were new synthesized compounds containing tetrazolate based ligands analogous to those investigated in Chapt. III. During the tests on a halogenated complex was unexpectedly evidenced the possibility to follow the kinetics of an electro-induced chemical reaction by using ECL signal. In the last chapter (V) the possibility to use mono-use silicon chips electrodes as ECL analitycal devices is under investigation. The chapter begins by describing the chip structure and materials then a signal reproducibility study and geometry optimization is carried on by using two different complexes. In the following paragraphs is reported in detail the synthesis of an ECL label based on Ru(bpy)3 2+ and the chip functionalization by using a lipoic acid SAM and the same label. After some preliminary characterizations (mass spectroscopy TOF) has been demonstrated that by mean of a simple and fast ECL measurement it’s possible to confirm the presence of the coupling product SAM-label into the chip with a very high sensitivity. No signal was detected from the same system by using photoluminescence.

Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

Concentration of hydrogen in hot brines of the Atlantis II Deep

An analysis of earlier measurements and author's data serves as a basis for a discussion of origin of deep-sea hydrogen. High hydrogen concentrations (0.001 ml/l or higher) in geothermal brines of the Atlantis II Deep depression are of abiogenic origin.

Optical in situ monitoring of hydrogen desorption from Ge(100) surfaces

Molecular hydrogen strongly interacts with vicinal Ge(100) surfaces during preparation in a metal organic vapor phase epitaxy reactor. According to X-ray photoemission spectroscopy and Fourier-transform infrared spectroscopy results, we identify two characteristic reflection anisotropy (RA) spectra for H-free and monohydride-terminated vicinal Ge(100) surfaces. RAS allows in situ monitoring of the surface termination and enables spectroscopic hydrogen kinetic desorption studies on the Ge(100) surface. Comparison of evaluated values for the activation energy and the pre-exponential factor of H desorption evaluated at different photon energies reflects that H unevenly affects the shape of the RA spectrum.

Van der Waals-corrected density functional theory: benchmarking for hydrogen-nanotube and nanotube-nanotube interactions

Density functional theory (DFT) is a powerful approach to electronic structure calculations in extended systems, but suffers currently from inadequate incorporation of long-range dispersion, or Van der Waals (VdW) interactions. VdW-corrected DFT is tested for interactions involving molecular hydrogen, graphite, single-walled carbon nanotubes (SWCNTs), and SWCNT bundles. The energy correction, based on an empirical London dispersion term with a damping function at short range, allows a reasonable physisorption energy and equilibrium distance to be obtained for H-2 on a model graphite surface. The VdW-corrected DFT calculation for an (8, 8) nanotube bundle reproduces accurately the experimental lattice constant. For H-2 inside or outside an (8, 8) SWCNT, we find the binding energies are respectively higher and lower than that on a graphite surface, correctly predicting the well known curvature effect. We conclude that the VdW correction is a very effective method for implementing DFT calculations, allowing a reliable description of both short-range chemical bonding and long-range dispersive interactions. The method will find powerful applications in areas of SWCNT research where empirical potential functions either have not been developed, or do not capture the necessary range of both dispersion and bonding interactions.

Significant quantum effects in hydrogen activation

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature reveal completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H2 up to ∼190 K and for D2 up to ∼140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.