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Neutron and muon characterisation techniques offer unique capabilities for investigating the complex structure and dynamics of rechargeable battery systems.

We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis (pentafluorophenyOboryl] phenyl -2, 2,6,6-tetrame-thylpiperidine (KCAT). The gas-solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H-2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4-200 K did not provide evidence for the formation of polarized H-2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H-2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H-2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H-2 diffusion into the FLP crystal with a rate-limiting movement of H-2 from inactive positions to reactive sites.

Populations rely on already present plastic responses (ancestral plasticity) and evolution (including both evolution of mean trait values, constitutive evolution, and evolution of plasticity) to adapt to novel environmental conditions. Because of the lack of evidence from natural populations, controversy remains regarding the interplay between ancestral plasticity and rapid evolution in driving responses to new stressors. We addressed this topic at the level of the metabolome utilizing a resurrected natural population of the water flea Daphnia magna that underwent a human-caused increase followed by a reduction in predation pressure within ~16 years. Predation risk induced plastic changes in the metabolome which were mainly related to shifts in amino acid and sugar metabolism, suggesting predation risk affected protein and sugar utilization to increase energy supply. Both the constitutive and plastic components of the metabolic profiles showed rapid, probably adaptive evolution whereby ancestral plasticity and evolution contributed nearly equally to the total changes of the metabolomes. The subpopulation that experienced the strongest fish predation pressure and showed the strongest phenotypic response, also showed the strongest metabolomic response to fish kairomones, both in terms of the number of responsive metabolites and in the amplitude of the multivariate metabolomic reaction norm. More importantly, the metabolites with higher ancestral plasticity showed stronger evolution of plasticity when predation pressure increased, while this pattern reversed when predation pressure relaxed. Our results therefore highlight that the evolution in response to a novel pressure in a natural population magnified the metabolomic plasticity to this stressor.

Tapia-Ruiz, Nuria et al., Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology., The authors gratefully acknowledge RS2E and Alistore-ERI for funding their research into Na-ion batteries. The funding received from the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 646433 (NAIADES), the Swedish Research Council, the Swedish Energy Agency (#37671-1), and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning (FORMAS), are all gratefully acknowledged. The many fruitful discussions within ALISTORE-ERI, and especially with M Rosa Palacín, have been most valuable. P J is also grateful for the continuous support from several of the Chalmers Areas of Advance: Materials Science and Energy. Funding from the European Union’s innovation program H2020 is acknowledged: H2020-MSCA-COFUND-2016 (DOC-FAM, Grant Agreement No. 754397). A Ponrouch is grateful to the Spanish Ministry for Economy, Industry and Competitiveness Severo Ochoa Programme for Centres of Excellence in R&D (SEV-2015-0496).

Accessing the intrinsic hydrogen content within ammonia, NH3, has the potential to play a very significant role in the future of a CO2-free sustainable energy supply. Inexpensive light metal imides and amides are effective at decomposing ammonia to hydrogen and nitrogen (2NH3 → 3H2 + N2), at modest temperatures, and thus represent a low-cost approach to on-demand hydrogen production. Building upon this discovery, this paper describes the integration of an ammonia cracking unit with a post-reactor gas purification system and a small-scale PEM fuel cell to create a first bench-top demonstrator for the production of hydrogen using light metal imides.

The development of a safe technique for the supply of hydrogen to small portable fuel cells has emerged as a significant barrier to their deployment in recent years, with solutions centering on the use of hydrogen absorption materials, or the generation of hydrogen through chemical reaction. In the present work we demonstrate that the ball-milling of Si under inert conditions in the presence of KOH and sucrose results in the formation of a fine Si-based powder which reacts spontaneously with water at ambient starting temperature to evolve hydrogen rapidly at high yield. Embedded KOH is capable of accelerating the hydrolysis reaction of silicon by the self-heating effect attributed to dissolution heat of KOH, obviating the need for external heating to initiate the reaction; it also reduces the sensitivity of the reaction to oxide contamination of the Si surface by enabling its dissolution in the form of soluble silicates. Moreover, the silicon–water reaction can be switched on and off by adjusting the ambient temperature. It is shown that ball-milled, KOH-embedded Si powder is able to react with different water sources, such as tap water, river water, and salt water, to produce H2 under aerobic conditions. The method represents a cheap scalable approach for the safe provision of hydrogen fuel to small fuel cells.

We have investigated ammonia adsorption in group two halides (MgI2 and CaBr2) using custom-built apparatus that permits simultaneous neutron diffraction, microwave dielectric characterisation and out-gas mass spectroscopy of solid state materials during ammonia adsorption. Deuterated ammonia was flowed over the sample and the uptake – as measured by mass flow meters, mass spectroscopy and structure – compared with the change in dielectric constant. An excellent correlation between ammonia content and dielectric property was observed and, when linked to diffraction, mass flow and mass spectroscopy data, could be used to determine the amount of ammonia present within the solid. The combination of these techniques could also be used to differentiate physisorbed and metal-coordinated ammonia and explain subtleties in the observed structural transformations.

Materials displaying the remarkable combination of high electrical conductivity and optical transparency already from the basis of many important technological applications, including flat panel displays, solar energy capture and other opto-electronic devices. Here we present the basic materials physics of these important materials centred on the nature of the doping process to generate n-type conductivity in transparent conducting oxides, the associated transition to the metallic (conducting) state and the detailed properties of the degenerate itinerant electron gas. The aim is to fully understand the origins of the basic performance limits of known materials and to set the scene for new or improved materials which will breach those limits for new-generation transparent conducting materials, either oxides, or beyond oxides.

Hydrogen has been identified as a fuel of choice for providing clean energy for transport and other applications across the world and the development of materials to store hydrogen efficiently and safely is crucial to this endeavour. Hydrogen has the largest scattering interaction with neutrons of all the elements in the periodic table making neutron scattering ideal for studying hydrogen storage materials. Simultaneous characterisation of the structure and dynamics of these materials during hydrogen uptake is straightforward using neutron scattering techniques. These studies will help us to understand the fundamental properties of hydrogen storage in realistic conditions and hence design new hydrogen storage materials. © 2009 Elsevier Ltd. All rights reserved.

Coaxial electrospinning was used to encapsulate the complex hydride ammonia borane in polystyrene to improve its properties as a hydrogen storage material. A solvent selection system was developed by using the Hansen solubility parameters to facilitate the choice of compatible solvents for core and shell. This enabled systematic optimization of the parameters needed for successful coelectrospinning. This approach has general application for any multiphase electrospinning system, including ones where the core is highly conducting or nonpolymeric. The resulting fiber morphologies depend strongly on the degree of miscibility of core and shell solutions. Fibers spun from immiscible core-shell solutions had a classic coaxial structure. Fibers produced from semimiscible core-shell solutions were highly porous, with inclusions extending through the fiber and an ordered radial and longitudinal distribution of nanoscale pores on the fiber surface. We suggest that this type of porosity may be due to an instability created in the nonaxisymmetric modes at the core-shell interface, resulting in intrusion of the core into the shell polymer. These controllably porous structures have numerous potential applications including materials templating or drug delivery. In the porous fibers, the temperature of the first hydrogen release of ammonia borane is reduced to 85 °C. This result suggests a nanostructured hydride, but a large mass loss indicates that much of the ammonia borane is expelled on heating. The coaxial fibers, in contrast, appear to encapsulate the hydride successfully. The coaxial and porous fibers alike showed no significant release of borazine, suggesting two different suppression mechanisms for this impurity. © 2010 American Chemical Society.

AgBr-BiOBr heterojunction photocatalysts with varying loadings of AgBr (0.5 wt%) lead to isolated AgBr species and reduced photocatalytic activity. Among such catalysts, the AgBr (0.2 wt%)-BiOBr exhibits the highest visible-light-responsive photoactivity, which can decolorize Rhodamine B within 30 min. However, these AgBr-BiOBr materials gradually lost their photoactivity in the cycling photocatalytic tests. Possible mechanisms for both the enhanced photocatalytic activity and deactivation of the AgBr-BiOBr heterojunctions were proposed on basis of theoretical speculation and experimental observations. © 2012 Elsevier Inc. All rights reserved.

A stepwise phase transition in the formation of lithium amidoborane via the solid-state reaction of lithium hydride and ammonia borane has been identified and investigated. Structural analyses reveal that a lithium amidoborane-ammonia borane complex (LiNH(2)BH(3).NH(3)BH(3)) and two allotropes of lithium amidoborane (denoted as alpha- and beta-LiNH(2)BH(3), both of which adopt orthorhombic symmetry) were formed in the process of synthesis. LiNH(2)BH(3).NH(3)BH(3) is the intermediate of the synthesis and adopts a monoclinic structure that features layered LiNH(2)BH(3) and NH(3)BH(3) molecules and contains both ionic and dihydrogen bonds. Unlike alpha-LiNH(2)BH(3), the units of the beta phase have two distinct Li(+) and [NH(2)BH(3)](-) environments. beta-LiNH(2)BH(3) can only be observed in energetic ball milling and transforms to alpha-LiNH(2)BH(3) upon extended milling. Both allotropes of LiNH(2)BH(3) exhibit similar thermal decomposition behavior, with 10.8 wt % H(2) released when heated to 180 degrees C; in contrast, LiNH(2)BH(3).NH(3)BH(3) releases approximately 14.3 wt % H(2) under the same conditions.

Colossal magnetoresistance manganites have been synthesised by the microwave dielectric heating of metal nitrates, which act both as effective microwave susceptors, and a ready source of oxidizing NO2 to induce mixed valency.

High quality, c-axis oriented thin films of semiconducting La{sub 2}CuO{sub 4} have been fabricated by pulsed laser-ablation deposition. Superconducting properties have been successfully induced in the films by a postdeposition, ex-situ static annealing process in a F{sub 2}/N{sub 2} gas mixture. The influence of the fluorination temperature on the structural, magnetic, and electronic properties of the resulting thin films has been examined in detail. X-ray data reveal that facile fluorination of the films proceeds via a complex, multistage process, often yielding to distinct La{sub 2}CuO{sub 4}-type phases. This phase segregation suggests a disproportionation process following fluorine uptake. Such a disproportionation is subtly different from that found for oxygen excess La{sub 2}CuO{sub 4} in that for La{sub 2}CuO{sub 4+{delta}} the parent O{sub 4} and an oxygen rich (O{sub 4+{delta}}) phase are formed, but in the present system two fluorinated (i.e., oxidized) phases are formed. La{sub 2}CuO{sub 4} thin films fluorinated at a temperature of 150 C possess the highest values for both T{sub c} (onset) (ca. 38.5 K) and critical current density (>10{sup 6} A cm{sup {minus}2} at 4.2 K in zero magnetic field). Magnetic susceptibility data demonstrate that this fluorination methodology is of sufficient sensitivity to allow the controlled hole-dopingmore » of semiconducting La{sub 2}CuO{sub 4} thin films through to the high-temperature superconducting regime.« less

Pulsed laser ablation has been used to fabricate La2CuO4 thin films. Superconducting properties have been successfully induced in the films by an ex-situ, post-ablation annealing process in F2 gas resulting in a Tc (onset) of 36 K. The presence of two slightly different c-axis expanded phases in the X-ray diffraction data of the fluorinated films implies a degree of inhomogeneity in F2 uptake. Critical current densities (Jc) and the irreversibility line have been established from hysteresis cycles. A Jc of ∼ 106 A cm−2 for a typical film was observed at 10 K in zero field.

The safe and efficient storage of hydrogen is widely recognized as one of the key technological challenges in the transition towards a hydrogen-based energy economy. Whereas hydrogen for transportation applications is currently stored using cryogenics or high pressure, there is substantial research and development activity in the use of novel condensed-phase hydride materials. However, the multiple-target criteria accepted as necessary for the successful implementation of such stores have not yet been met by any single material. Ammonia borane, NH3BH3, is one of a number of condensed-phase compounds that have received significant attention because of its reported release of approximately 12 wt% hydrogen at moderate temperatures (approximately 150 degrees C). However, the hydrogen purity suffers from the release of trace quantities of borazine. Here, we report that the related alkali-metal amidoboranes, LiNH2BH3 and NaNH2BH3, release approximately 10.9 wt% and approximately 7.5 wt% hydrogen, respectively, at significantly lower temperatures (approximately 90 degrees C) with no borazine emission. The low-temperature release of a large amount of hydrogen is significant and provides the potential to fulfil many of the principal criteria required for an on-board hydrogen store.

We compute the hydrogen vibrational spectra for bulk ammonia borane (NH 3BH 3), for both protonated and deuterated cases, using harmonic and anharmonic methodologies as well as low frequency coupling and quantifying dispersive effects to understand their influence on the resulting spectra. Even at 10 K the accounting of anharmonic effects on the incoherent inelastic neutron scattering (IINS) signal is more significant than approximations introduced by sampling and interpolating a finite simulation cell to capture dispersion effects. We compare our computed anharmonic spectrum with IINS measurements and find excellent agreement. © 2012 American Chemical Society.

We report an investigation of the synthesis of a cobalt aluminate spinel composite from the heat-induced collapse of cobalt ion-exchanged sodium zeolite X. The work presented here adds to earlier studies by illustrating that by careful control of synthesis and reaction conditions, both the phase composition and crystallite size of the spinel can be controlled. The spinel crystallites grow within siliceous materials formed by the collapse of the zeolite framework, with the crystalline particles being completly shrouded by the siliceous matrix. © 2005 Elsevier Ltd. All rights reserved.

Highly conductive (> 103 Ω-1cm-1) and transparent (∼ 90%) In4Sn3O12 films have been deposited using pulsed laser deposition (PLD) on glass substrates held at a temperature of 500°C under varying pressures of oxygen (2.5 mTorr ≤ PO2 ≤ 15 mTorr). The crystallinity and the roughness of the films were found to increase with the pressure of oxygen used during deposition. Electron concentrations of the order of 5×1020 cm-3 and mobilities as high as 30 cm2V-1s-1 were derived from the measurement of Hall coefficients. Both the electronic transport and optical properties of the films were found to be strongly sensitive to the pressure of oxygen used during deposition.

The temperature dependence of the magnetic shifts in the normal state of the anion-doped superconductor Nd2CuO3.7F0.3 are presented. The shifts due to the neodymium moments are subtracted off, to leave magnetic hyperfine shifts with a linear temperature dependence. In contrast to YBCO the temperature-dependent term in the shift for B applied parallel to the c-axis of the tetragonal crystal is about seven times larger than the shift when B is applied perpendicular to the c-axis.

Transmission electron microscopy has been used to characterise the microstructures of Sr2Cr0.5CuO2 precursor thin films and annealed Hg0.5Cr0.5Sr2CuO4+δ thin films on (0 0 1) SrTiO3 substrates. Precursor films consist essentially of amorphous Sr2CuO3 phase with SrCrxCuO2 grains embedded, while Hg0.5Cr0.5Sr2CuO4+δ films are epitaxial with the orientation relationship (0 0 1) Hg ∥(0 0 1) STO , [1 0 0] Hg ∥[1 0 0] STO . Hg and Cr diffuse through the whole film thickness. Some a-axis grains are present in the Hg0.5Cr0.5Sr2CuO4+δ films with much lower Hg and Cr contents.

A comparison of the Sr solubility limits in bulk YBa2Cu3O7 and thin film YBa2Cu3O7 has been made. Whereas for the former, single phase samples of YBa2−xSrxCu3O7 are only formed for 0≤x≤1.0 the thin films show a higher solubility range, 0≤x≤1.6. Both the c parameter and Tc decrease with increasing x, and the Sr content of the films has been confirmed by EDAX. These results demonstrate the potential of laser ablation for the synthesis of new and modified oxide superconductors.

Thin films of In2 O3 have been grown on Y-stabilized Zr O2 (100) by oxygen plasma assisted molecular beam epitaxy with a substrate temperature of 650 °C. Ordered epitaxial growth was confirmed by high resolution transmission electron microscopy. The position of the valence band onset in the x-ray photoemission spectra of the epitaxial films is found to be inconsistent with the widely quoted value of 3.75 eV for the fundamental bandgap of In2 O3 and suggests a revised value of 2.67 eV. © 2008 American Institute of Physics.

Ni/Al2O3, Co/Al2O3 and bimetallic Ni(Co)/Al2O3 catalysts were prepared using an impregnation method and employed in CO2 dry reforming of methane under coking-favored conditions. The spent catalysts were carefully characterized using typical characterization technologies and inelastic neutron scattering spectroscopy. The bimetallic catalyst exhibited a superior activity and anti-coking performance compared to Ni/Al2O3, while the most resistant to coking behavior was Co/Al2O3. The enhanced activity of the Ni(Co)/Al2O3 bimetallic catalyst is attributed to the reduced particle size of metallic species and resistance to forming stable filamentous carbon. The overall carbon deposition on the spent bimetallic catalyst is comparable to that of the spent Ni/Al2O3 catalyst, whereas the carbon deposited on the bimetallic catalyst is mainly less-stable carbonaceous species as confirmed by SEM, TPO, Raman and INS characterization. This study provides an in depth understanding of alloy effects in catalysts, the chemical nature of coked carbon on spent Ni-based catalysts and, hopefully, inspires the creative design of a new bimetallic catalyst for dry reforming reactions.

Flake-like BiOBr semiconductors have been prepared using hydrothermal synthesis with meticulous control of synthesis parameters and used for photocatalytic degradation of methyl orange. XRD, SEM and UV-vis characterizations have been performed to study the obtained BiOBr materials. The results indicate that the morphology and crystallite size of BiOBr depend significantly on the temperature and duration of the hydrothermal syntheses. Diffuse UV-vis spectra show the BiOBr materials to be indirect semiconductors with an optical bandgap of approximately 2.92 eV, which is essentially unaffected by the synthesis parameters. The hydrothermal-synthesized BiOBr flakes exhibit noticeable activity for photodegradation of methyl orange under visible light (>400 nm) illumination, with the BiOBr synthesized by hydrothermal treatment at 120 degrees C for 6 h exhibiting superior photocatalytic performance in these flakes. The excellent activity and photo-stability reveal that BiOBr is a promising visible-light-responsive photocatalyst. (C) 2010 Elsevier B.V. All rights reserved.

Co(x)Mg(3-x)/Al composite oxides (xCoMAO-800) were prepared by calcination of Co(x)Mg(3-x)/Al hydrotalcites (x = 0.0, 0.5,1.0,1.5,2.0,2.5,3.0, respectively) at 800 degrees C. The materials were characterized using XRD, TG-DSC, N(2) adsorption-desorption and TPR. The methane catalytic combustion over the xCoMAO-800 was assessed in a fixed bed micro-reactor. The results revealed that cobalt can be homogenously dispersed into the matrices of the hydrotalcites and determines the structure, specific surface areas and porosity of the derived xCoMAO-800 oxide catalysts. The thermal stability and homogeneity of the hydrotalcites markedly depends on the cobalt concentration in the hydrotalcites. The Co-based hydrotalcite-derived oxides exhibit good activity in the catalytic combustion of methane. The catalytic activity over the xCoMAO-800 oxides enhances with increasing x up to 1.5, but subsequently decreases dramatically as cobalt loadings are further increased. The 1.5CoMAO-800 catalyst shows the best methane combustion activity, igniting methane at 450 degrees C and completing methane combustion around 600 degrees C. The catalytic combustion activity over the xCoMAO-800 oxides are closely related to the strong Co-Mg/Al interaction within the mixed oxides according to the TG-DSC, TPR and activity characteristics. (C) 2009 Elsevier B.V. All rights reserved.

Lithium borohydride absorbs anhydrous ammonia to form four stable ammoniates; Li(NH(3))(n)BH(4), mono-, di-, tri-, and tertraammoniate. This paper focuses on the monoammoniate, Li(NH(3))BH(4), which is readily formed on exposure of LiBH(4) to ammonia at room temperature and pressure. Ammonia loss from Li(NH(3))BH(4) commences around 40 degrees C and the compound transforms directly to LiBH(4). The crystal structure of Li(NH(3))BH(4) is reported here for the first time. Its close structural relationship with LiBH(4) provides a clear insight into the facile nature and mechanism of ammonia uptake and loss. These materials not only represent an excellent high weight-percent ammonia system but are also potentially important hydrogen stores.

Nanostructured hydrogenated graphite (CnanoHx) was synthesized here from graphite by ball-milling under a hydrogen (H2) atmosphere. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and transmission electron microscopy (TEM) show that ball milling results in the rupture of graphene sheets creating active defects and allowing hydrogen to be dissociated and then chemisorbed. Most likely small quantities of iron particles incorporated during the milling process act as a catalyst. C nanoHx thus possesses unique characteristic hydrogenated states present in nanometer scale particles, unlike standard hydride materials. Electron spin resonance (ESR) spectroscopy resolves two distinct paramagnetic components. The first is assigned to (intrinsic) delocalized π-electrons in the graphene sheets (g ~ 2.008) which disappears after approximately 32 h milling. The second ESR component grows in intensity with milling time and is assigned to localized electrons (g ~ 2.003) with a concentration of 3 × 1020 spins per gram after 80 h milling. HYSCORE spectroscopy reveals proton hyperfine couplings, and variable temperature CW ESR spectra demonstrate an unexpected magnetic ordering at low temperatures (~ 10 K). Formation of CnanoHx thus consists of weakly coupled localized electrons with wave functions that extends over small graphitic moieties. The radical centers do not physisorb a large quantity of H2 molecules under conditions required for practical H2 storage materials and are a product of the milling process and chemisorption of hydrogen. © 2009 American Chemical Society.

Ni-based catalysts derived from Ni-Mg/Al ternary hydrotalcites with low Ni-loadings have been prepared for the partial oxidation of methane (POM) to syngas. The reducibility, surface basicity, and effects of catalyst reduction on POM reactivity over these catalysts have been explored. Temperature-programmed reduction and CO2-temperature-programmed desorption results indicate that the amount of Ni-loading and the Mg/Al molar ratio exert a remarkable influence on their reducibility but have little influence on the surface basicity, with an increase in Mg/Al ratio also lessening the base strength of the alkaline sites. Reaction temperature significantly affects the reactivity of the catalysts, and high temperature reduction of the catalysts can lead to superior reactivity to those reduced at low temperature. An in situ reduction of the catalyst has been observed in the POM reaction for catalysts reduced at low temperature. Under the optimized reaction conditions, the catalysts with Ni content from 8 wt % to 15.5 wt % show similar activity in POM reactions, and this activity is much higher than for catalysts with lower Ni-loading (̃4 wt %), which is explained in terms of nickel reducibility and the surface basicity of the catalysts. © 2009 American Chemical Society.

We demonstrate that the ammonia decomposition reaction catalysed by sodium amide proceeds under a different mechanism to ammonia decomposition over transition metal catalysts. Isotopic variants of ammonia and sodium amide reveal a significant kinetic isotope effect in contrast to the nickel-catalysed reaction where there is no such effect. The bulk composition of the catalyst is also shown to affect the kinetics of the ammonia decomposition reaction.

The non-stoichiometric lithium imide–amide system effectively decomposes ammonia to its constituents, hydrogen and nitrogen. Isotopic studies show that this bulk catalytic reaction has the potential to generate high-purity hydrogen for future energy and transport applications., We demonstrate that non-stoichiometric lithium imide is a highly active catalyst for the production of high-purity hydrogen from ammonia, with superior ammonia decomposition activity to a number of other catalyst materials. Neutron powder diffraction measurements reveal that the catalyst deviates from pure imide stoichiometry under ammonia flow, with active catalytic behaviour observed across a range of stoichiometry values near the imide. These measurements also show that hydrogen from the ammonia is exchanged with, and incorporated into, the bulk catalyst material, in a significant departure from existing ammonia decomposition catalysts. The efficacy of the lithium imide–amide system not only represents a more promising catalyst system, but also broadens the range of candidates for amide-based ammonia decomposition to include those that form imides.

In this paper we develop a simple model based on a leaky transmission line to assess the electrical performance of transparent current spreading layers for application to surface light emitting diodes. Figures of merit suitable for device design are obtained and these are applied to a range of material systems reported in the literature. These calculations show that materials with electrical characteristics approaching ultimate performance limits can be achieved. Furthermore, calculations of the electromagnetic absorption of conducting layers show that further improvements should be possible by selecting materials with the highest possible majority carrier mobilities, which enable films of greater thickness to be grown while maintaining high transparency, leading to very low spreading layer resistances. Ways of achieving improved mobility are also discussed.

The location of hydrogen within Ti–Cr–V–Mo alloys has been investigated during hydrogen absorption and desorption using in situ neutron powder diffraction and inelastic neutron scattering. Neutron powder diffraction identifies a low hydrogen equilibration pressure body-centred tetragonal phase that undergoes a martensitic phase transition to a face-centred cubic phase at high hydrogen equilibration pressures. The average location of the hydrogen in each phase has been identified from the neutron powder diffraction data although inelastic neutron scattering combined with density functional theory calculations show that the local structure is more complex than it appears from the average structure. Furthermore the origin of the change in dissociation pressure and hydrogen trapping on cycling in Ti–Cr–V–Mo alloys is discussed.

This paper presents a new type of process for the cracking of ammonia (NH3) that is an alternative to the use of rare or transition metal catalysts. Effecting the decomposition of NH3 using the concurrent stoichiometric decomposition and regeneration of sodium amide (NaNH2) via sodium metal (Na), this represents a significant departure in reaction mechanism compared with traditional surface catalysts. In variable-temperature NH3 decomposition experiments, using a simple flow reactor, the Na/NaNH2 system shows superior performance to supported nickel and ruthenium catalysts, reaching 99.2% decomposition efficiency with 0.5 g of NaNH2 in a 60 sccm NH3 flow at 530 °C. As an abundant and inexpensive material, the development of NaNH2-based NH3 cracking systems may promote the utilization of NH3 for sustainable energy storage purposes.

We report the experimental investigation of hydrogen storage and release in the lithium amide-lithium hydride composite (Li-N-H) system. Investigation of hydrogenation and dehydrogenation reactions of the system through in situ synchrotron X-ray powder diffraction experiments allowed for the observation of the formation and evolution of non-stoichiometric intermediate species of the form Li1+xNH2-x. This result is consistent with the proposed Frenkel-defect mechanism for these reactions. We observed capacity loss with decreasing temperature through decreased levels of lithium-rich (0.7 ≤ x ≤ 1.0) non-stoichiometric phases in the dehydrogenated material, but only minor changes due to multiple cycles at the same temperature. Annealing of dehydrogenated samples reveals the reduced stability of intermediate stoichiometry values (0.4 ≤ x ≤ 0.7) compared with the end member species: lithium amide (LiNH2) and lithium imide (Li2NH). Our results highlight the central role of ionic mobility in understanding temperature limitations, capacity loss and facile reversibility of the Li-N-H system.

The synthesis of the magnesium halide ammines (Mg(NH)Cl, Mg(NH)Br and Mg(NH)I) is reported and their structures are identified by high resolution X-ray diffraction. The structures of Mg(NH)Br and Mg(NH)I are reported for the first time. The desorption properties of Mg(NH)Cl, Mg(NH)Br and Mg(NH)I are examined by thermogravimetric analysis and NMR, and the trends in desorption properties as a function of composition are interpreted using a simple ionic model. It is found that the desorption properties are dependent on the lattice enthalpy of the intermediate and final phases Mg(NH)X, Mg(NH)X and MgX, that the anion has limited effect on the state of Mg-N bonding and that the desorption temperature of ionic ammines may be tuned by varying the size of the anion. © 2013 Elsevier B.V. All rights reserved.

We have observed a superstructure derived from the compound Tl0.75Sr1.8Ba0.2CuO(y). This compound arises from the 'collapse' of the parent oxynitrate compound TlSr2Ba2Cu2O7 (NO3) under controlled thermal decomposition. A combined X-ray and neutron powder diffraction study of the title compound indicates that the superstructure possesses the Pmmm space group, with unit cell parameters (derived from neutron diffraction data) of a = 3.7362(3) Å, b = 11.5449(9) Å, and c = 9.1494(8) Å. This superstructure takes the form of a three-fold repeat along the crystal b-axis produced through local distortions of the thallium and barium/strontium positions. This compound is nonsuperconducting due to the presence of a large number of vacancies in the electronically active copper-oxygen planes. (C) 2000 academic Press.

(1)H, (7)Li, (14)N, and (23)Na high resolution nuclear magnetic resonance (NMR) measurements are reported for fluid solutions of lithium and sodium in anhydrous liquid ammonia across the metal-to-nonmetal transition (MNM transition), paying particular attention to the phenomenon of liquid-liquid phase separation which occurs in the composition/temperature region close to the MNM transition. Our results are discussed in terms of the electronic structure of fluid metal-ammonia solutions at low temperatures (ca. 240 K). We find that the electronic phase transition to the metallic state in these solutions, especially at temperatures close to the liquid-liquid critical consolute temperature, occurs from a nonmetallic, electrolytic solution containing a predominance of electron spin-paired, (diamagnetic) charged bosonic states. The possible implications of these observations to the nature of the liquid-liquid phase separation are discussed, both from the views of N. F. Mott, regarding the MNM transition in sodium-ammonia solutions, and those of R. A. Ogg, regarding the possibility of high-temperature superconductivity in these solutions. Similarities between the electronic structure of metal-ammonia solutions and the high-temperature cuprate superconductors are also briefly emphasized.

We thank ISIS for the time on GEM, Winfried Kockelmann for his assistance during data collection, the ISIS Sample Environment Section, and in particular Mark Kibble, for their help in facilitating the experiment, and Mr. Katsuhiko Hirose, Prof. Peter Edwards and Dr. Andrew Taylor for their support. © 2013 WILEY-VCH Verlag GmbH and Co.

Complex hydrides such as LiBH4 and LiNH2 exceed the gravimetric hydrogen density of transition metal hydrides by one order of magnitude. However, hydrogen in complex hydrides is covalently bound and arranged in subunits e.g. [NH2]- and [BH4] - with a fixed stoichiometry. Along this line of thought, these compounds can be considered as ordinary ionic compounds. The corresponding pseudo-binary phase diagram comprises a great variety of phases with a high ionic mobility of Li-cations as well as pseudo-anions as measured by diffusion gradients. Using this equilibrium preparation method, we are able to discriminate between stable and meta-stable phases such as Li2BH 4NH2 formed during high-energy ball-milling. We identify Li2BH4NH2 as a mobile intermediate during phase formation. Hydrogen desorption as relevant for their potential use as hydrogen storage does not take place below 200°C as measured by gravimetry. In particular amides, but also borohydrides emit hydrogen, and nitrogen and boron, respectively, containing species (NH3 and BHx, respectively). We probe the bulk and surface exchange of hydrogen in such subunits in LiNH2 and Li2BH4NH2 by hydrogen-deuterium experiments. In contrast to bulk exchange, surface exchange processes occur at very low temperatures - lower than a significant decomposition rate but coincidentally with the appearance of Li2NH comprising high ionic conductivity. The rate limiting step is thus the bulk transport - in agreement with the empirical correlation that the mobility of ions is linked to the hydrogen desorption kinetics of a material (P. A. Anderson et al., Faraday Discuss., 2011, 151, 271-284). However, the bulk transport of ionic species competes with the diffusion of neutral species such as ammonia, being the origin of the unwanted emission of NH3. These results are discussed with respect to the ionic mobility of borohydride and amide materials. © 2012 The Royal Society of Chemistry.

HyStorM is a multidisciplinary hydrogen-storage project aiming to synthesise and tune materials hydrogen storage properties for automotive applications. Firstly, unique high-throughput combinatorial thin-film technologies are used to screen materials' hydrogen storage properties. Then promising thin-film candidate compositions are synthesised and examined in the bulk. In this paper, we report on our results within the ternary compositions Mg-Ti-B and Ca-Ti-B. Primary screening of the Mg-Ti-B ternary identified a high capacity hotspot corresponding to Mg0.36Ti0.06B0.58, with 10.6 wt% H2 capacity. Partial reversibility has been observed for this material in the thin-film. Bulk Ti-doped Mg(BH4)2 composites show rehydrogenation to MgH2 under the conditions used. The synthesised thin-film Ca-Ti-B ternary showed only low hydrogen storage capacities. In the bulk, Ti-doping experiments on Ca(BH4)2 demonstrated reversible storage capacities up to 5.9 wt% H2. Further characterisation experiments are required to decipher the role of the Ti-dopant in these systems in both films and in the bulk.

In this paper we present the orientation dependence of the copper nmr spectra in the Nd2CuO4−xFx system. The experiments were undertaken on both aligned and random powder samples. Initial nmr results indicated that the c-axis was aligned perpendicular to the magnetic field that was applied during the alignment process. This was subsequently confirmed by X-ray diffraction. The room temperature 63Cu nmr data was fitted using this distribution and this revealed that v Q was at most 6 MHz, Kax=0.15 ± 0.02%, Kiso=0.40 ± 0.05%. Once again, as in previous studies, we found that the indications on the degree of alignment obtained from X-ray measurements was substantially greater than the indications from the nmr data; X-ray measurements indicated nearly 100% alignment, nmr studies indicated 70% alignment. We speculate that the X-ray technique is not sensitive to large unaligned clumps in the samples as they are prepared.

Lead dioxide has been used for over a century in the lead-acid battery. Many fundamental questions concerning PbO(2) remain unanswered, principally: (i) is the bulk material a metal or a semiconductor, and (ii) what is the source of the high levels of conductivity? We calculate the electronic structure and defect physics of PbO(2), using a hybrid density functional, and show that it is an n-type semiconductor with a small indirect band gap of similar to 0.2 eV. The origin of electron carriers in the undoped material is found to be oxygen vacancies, which forms a donor state resonant in the conduction band. A dipole-forbidden band gap combined with a large carrier induced Moss-Burstein shift results in a large effective optical band gap. The model is supported by neutron diffraction, which reveals that the oxygen sublattice is only 98.4% occupied, thus confirming oxygen substoichiometry as the electron source.

We have synthesized a single crystal of lithium amide (LiNH2, LiND2) by melting method, and performed neutron diffraction of the single crystal at variable temperature. LiND2 is tetragonal structure and I-4 space group. Lattice parameters and unit cell volume of LiND 2 at room temperature, 50 °C, 100 °C, 150 °C and 200 °C were determined. Both of the lattice parameters and the unit cell volume increase with increase of temperature. From these results, we have estimated coefficient of volumetric thermal expansion αV of LiND 2 to be 222 × 10-6/K. With increase of temperature, all thermal ellipsoids gradually expand because of thermal vibration. © 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights.

An ultrasound-assisted, precipitation-deposition method has been developed to synthesise visible-light-responsive BiOBr-ZnFe(2)O(4) heterojunction photocatalysts. The heterojunctions with suitable BiOBr/ZnFe(2)O(4) ratios have a fascinating micro-spherical morphology and exhibit exceptional photocatalytic activity in visible-light degradation of Rhodamine B.