Rapid synthesis of porous honeycomb Cu/Pd through a hydrogen-bubble templating method

A rapid electrochemical method based on using a clean hydrogen-bubble template to form a bimetallic porous honeycomb Cu/Pd structure has been investigated. The addition of palladium salt to a copper-plating bath under conditions of vigorous hydrogen evolution was found to influence the pore size and bulk concentration of copper and palladium in the honeycomb bimetallic structure. The surface was characterised by X-ray photoelectron spectroscopy, which revealed that the surface of honeycomb Cu/Pd was found to be rich with a Cu/Pd alloy. The inclusion of palladium in the bimetallic structure not only influenced the pore size, but also modified the dendritic nature of the internal wall structure of the parent copper material into small nanometre-sized crystallites. The chemical composition of the bimetallic structure and substantial morphology changes were found to significantly influence the surface-enhanced Raman spectroscopic response for immobilised rhodamine B and the hydrogen-evolution reaction. The ability to create free-standing films of this honeycomb material may also have many advantages in the areas of gas- and liquid-phase heterogeneous catalysis.

Monitoring cuprous ion transport by scanning electrochemical microscopy during the course of copper electrodeposition

Scanning electrochemical microscopy (SECM), in the substrate generation–tip collection (SG-TC) mode, has been used to detect the cuprous ion intermediate formed during the course of electrodeposition of Cu metal from aqueous solution. Addition of chloride is confirmed to strongly stabilize the ion in aqueous solution and enhance the rate of Cu electrodeposition. This SECM method in the SG-TC mode offers an alternative to the rotating ring disk electrode (RRDE) technique for in situ studies on the effect of plating bath additives in metal electrodeposition. An attractive feature of the SECM relative to the RRDE method is that it allows qualitative aspects of the electrodeposition process to be studied in close proximity to the substrate in a simple and direct fashion using an inexpensive probe, and without the need for forced convection.

Observation of ions and particles near busy roads using a Neutral Cluster and Air Ion Spectrometer (NAIS)

Motor vehicles emit large quantities of ions in the form of both charged particles and molecular cluster ions. While, the health effects of inhalation of charged particles is largely unexplored, the concentrations near busy roads and the distance to which these particles and ions are carried have important implications for the exposure of the large percentage of the population that lives close to such roadways. We measured ion concentrations using a neutral cluster and air ion spectrometer (NAIS) near seven busy roads carrying on the average approximately 7000 vehicles hr-1 including about 15% heavy duty diesel vehicles. In this study, charged particle concentrations were measured as a function of downwind distance from the road for the first time. We show that, at a moderate wind speed of 2.0 m s-1, mean charged particle concentrations at the kerb were of the order of 2x104 cm-3 and, more importantly, decreased as d 0.6 where d is the distance from the road. While cluster ions were rapidly depleted by attachment to particles and were not carried to more than about 20 m from the road, elevated concentrations of charged particle were detected up to at least 400 m from the road. Most of the charge on the downwind side was carried on the larger particles, with no excess charge on particles smaller than about 10 nm. At 30 nm, particles carried more than double the charge they would normally carry in equilibrium. There are very few measurements of ions near road traffic and this is the first study of the spatial dispersion of charged particles from a road.

Hexagon platinum Schottky contact with ZnO thin film for hydrogen sensing

This paper reports on the study of the effect on adding total peripheries and sharp edges to the Schottky contact as a hydrogen sensor. Schottky contact was successfully designed and fabricated as hexagon-shape. The contact was integrated together with zinc oxide thin film and tested towards 1% hydrogen gas. Simulations of the design were conducted using COMSOL Multiphysics to observe the electric field characteristic at the contact layer. The simulation results show higher electric field induced at sharp edges with 4.18×104 V/m. Current-voltage characteristic shows 0.27 V voltage shift at 40 μA biased current.

Mechanism of ferromagnetism in non-magnetic ion-doped zinc oxides

Zinc oxide (ZnO) that contains non-magnetic ionic dopants, such as nitrogen (N)-doped zinc oxide (ZnO:N), has been observed to exhibit ferromagnetism. Ferromagnetism is proposed to arise from the Coulomb excitation in the localized states that is induced by the oxygen vacancy, V O. A model based on the Coulomb excitation that is associated with the electron–phonon interaction theoretically explains the ferromagnetic mechanism of ZnO:N. This study reveals that the ferromagnetism will be induced by either deep localized states with a small V O concentration or shallow localized states with a high V O concentration. Additionally, electron–phonon coupling either suppresses the ferromagnetism that is induced by the deep donor states of V O or enhances the ferromagnetism that is induced by the shallow donor states of V O.

A comparison study on hydrogen sensing performance of MoO3 nanoplatelets coated with a thin layer of Ta2O5 or La2O3

There has been significant interest in developing metal oxide films with high surface area-to-volume ratio nanostructures particularly in substantially increasing the performance of Pt/oxide/semiconductor Schottky-diode gas sensors. While retaining the surface morphology of these devices, they can be further improved by modifying their nanostructured surface with a thin metal oxide layer. In this work, we analyse and compare the electrical and hydrogen-sensing properties of MoO3 nanoplatelets coated with a 4 nm layer of tantalum oxide (Ta2O5) or lanthanum oxide (La2O3). We explain in our study, that the presence of numerous defect traps at the surface (and the bulk) of the thin high-� layer causes a substantial trapping of charge during hydrogen adsorption. As a result, the interface between the Pt electrode and the thin oxide layer becomes highly polarised. Measurement results also show that the nanoplatelets coated with Ta2O5 can enable the device to be more sensitive (a larger voltage shift under hydrogen exposure) than those coated with La2O3.

UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

UV-vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag-2 (+) is compared with a literature spectrum as a further benchmark.

Ultraviolet Photodissociation of the N-Methylpyridinium Ion: Action Spectroscopy and Product Characterization

The ultraviolet photodissociation of gas-phase N-methylpyridinium ions is studied at room temperature using laser photodissociation mass spectrometry and structurally diagnostic ion-molecule reaction kinetics. The C5H5N-CH3+ (m/z 94), C5H5N-CD3+ (m/z 97), and C5D5N-CH3+(m/z 99) isotopologues are investigated, and it is shown that the N-methylpyridinium ion photodissociates by the loss of methane in the 36 000 - 43 000 cm(-1) (280 - 230 nm) region. The dissociation likely occurs on the ground state surface following internal conversion from the SI state. For each isotopologue, by monitoring the photofragmentation yield as a function of photon wavenumber, a broad vibronically featured band is recorded with origin (0-0) transitions assigned at 38 130, 38 140 and 38 320 cm(-1) for C5H5N-CH3+ C5H5N-CD3+ and C5D5N-CH3+, respectively. With the aid of quantum chemical calculations (CASSCF(6,6)/aug-cc-pVDZ), most of the observed vibronic detail is assigned to two in-plane ring deformation modes. Finally, using ion-molecule reactions, the methane coproduct at m/z 78 is confirmed as a 2-pyridinylium ion.

Gas-Phase Transformation of Phosphatidylcholine Cations to Structurally Informative Anions via Ion/Ion Chemistry

Gas-phase transformation of synthetic phosphatidylcholine (PC) monocations to structurally informative anions is demonstrated via ion/ion reactions with doubly deprotonated 1,4-phenylenedipropionic acid (PDPA). Two synthetic PC isomers, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (PC16:0/18:1) and 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (PC18:1/16:0), were subjected to this ion/ion chemistry. The product of the ion/ion reaction is a negatively charged complex, \[PC + PDPA - H](-). Collisional activation of the long-lived complex causes transfer of a proton and methyl cation to PDPA, generating \[PC - CH3](-). Subsequent collisional activation of the demethylated PC anions produces abundant fatty acid carboxylate anions and low-abundance acyl neutral losses as free acids and ketenes. Product ion spectra of \[PC - CH3](-) suggest favorable cleavage at the sn-2 position over the sn-1 due to distinct differences in the relative abundances. In contrast, collisional activation of PC cations is absent of abundant fatty acid chain-related product ions and typically indicates only the lipid class via formation of the phosphocholine cation. A solution phase method to produce the gas-phase adducted PC anion is also demonstrated. Product ion spectra derived from the solution phase method are similar to the results generated via ion/ion chemistry. This work demonstrates a gas-phase means to increase structural characterization of phosphatidylcholines via ion/ion chemistry. Grant Number ARC/CE0561607, ARC/DP120102922

Isolation and characterization of charge-tagged phenylperoxyl radicals in the gas phase : direct evidence for products and pathways in low temperature benzene oxidation

The phenylperoxyl radical has long been accepted as a critical intermediate in the oxidation of benzene and an archetype for arylperoxyl radicals in combustion and atmospheric chemistry. Despite being central to many contemporary mechanisms underpinning these chemistries, reports of the direct detection or isolation of phenylperoxyl radicals are rare and there is little experimental evidence connecting this intermediate with expected product channels. We have prepared and isolated two charge-tagged phenyl radical models in the gas phase [i.e., 4-(N,N,N-trimethylammonium) phenyl radical cation and 4-carboxylatophenyl radical anion] and observed their reactions with dioxygen by ion-trap mass spectrometry. Measured reaction rates show good agreement with prior reports for the neutral system (k(2)[(Me3N+)C6H4 center dot + O-2] = 2.8 x 10(-11) cm(3) molecule(-1) s(-1), Phi = 4.9%; k(2)[(-O2C)C6H4 center dot + O-2] = 5.4 x 10(-1)1 cm(3) molecule(-1) s(-1), Phi = 9.2%) and the resulting mass spectra provide unequivocal evidence for the formation of phenylperoxyl radicals. Collisional activation of isolated phenylperoxyl radicals reveals unimolecular decomposition by three pathways: (i) loss of dioxygen to reform the initial phenyl radical; (ii) loss of atomic oxygen yielding a phenoxyl radical; and (iii) ejection of the formyl radical to give cyclopentadienone. Stable isotope labeling confirms these assignments. Quantum chemical calculations for both charge-tagged and neutral phenylperoxyl radicals confirm that loss of formyl radical is accessible both thermodynamically and entropically and competitive with direct loss of both hydrogen atom and carbon dioxide.

Ion-molecule reactions reveal facile radical migration in peptides

Ion-molecule reactions between molecular oxygen and peptide radicals in the gas phase demonstrate that radical migration occurs easily within large biomolecules without addition of collisional activation energy.

Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Pilot plant studies of ion exchange for desalination of coal seam gas produced water

This paper reports a study of ion exchange (IX) as an alternative CSG water treatment to the widely used reverse osmosis (RO) desalination process. An IX pilot plant facility has been constructed and operated using both synthetic and real CSG water samples. Application of appropriate synthetic resin technology has proved the effectiveness of IX processes.

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.

Mass spectrometric study of the dissociation of Group XI metal complexes with fatty acids and glycerolipids : Ag2H+ and Cu2H+ ion formation in the presence of a double bond

Results of mass spectrometric studies are reported for the collisional dissociation of Group XI (Cu, Ag, Au) metal ion complexes with fatty acids (palmitic, oleic, linoleic and a-linolenic) and glycerolipids. Remarkably, the formation of M2H+ ions (M = Cu, Ag) is observed as a dissociation product of the ion complexes containing more than one metal cation and only if the lipid in the complex contains a double bond. Ag2H+ is formed as the main dissociation channel for all three of the fatty acids containing double bonds that were investigated while Cu2H+ is formed with one of the fatty acids and, although abundant, is not the dominant dissociation channel. Also. Cu(I) and Ag(I) ion complexes were observed with glycerolipids (including triacylglycerols and glycerophospholipids) containing either saturated or unsaturated fatty acid substituents. Interestingly. Ag2H+ ion is formed in a major fragmentation channel with the lipids that are able to form the complex with two metal cations (triacylglycerols and glycerophosphoglycerols), while lipids containing a fixed positive charge (glycerophospocholines) complex only with a single metal cation. The formation of Ag2H+ ion is a significant dissociation channel from the complex ion Ag-2(L-H)(+) where L = Glycerophospholipid (GP) (18:1/18:1). Cu(I) also forms complexes of two metal cations with glycerophospholipids but these do not produce Cu2H+ upon dissociation. Rather organic fragments, not containing Cu(I), are formed, perhaps due to different interactions of these metal cations with lipids resulting from the much smaller ionic radius of Cu(I) compared to Ag(I) (C).