29Si, 27Al MAS NMR is used to characterize Laponite RD and synthetic saponites of variable interlayer charge. The Si/Al ratios are in good agreement with the calculated charge from chemical analysis except for the lowest-charged saponite. In contrast to the 29Si MAS NMR spectra in which resolved signals are detected, the 27Al MAS NMR spectra show one signal whose linewidth increases with the clay charge. The water content of the clay samples was obtained from 1H MAS NMR.

The 2D MQMAS NMR technique is required to obtain a high-resolution spectrum of nuclei with strong quadrupolar interaction. This method was applied to the 23Na nucleus of clay counterions and to the 27Al structural nucleus. One well-defined 23Na NMR signal is observed for all the clays studied except the highest-charged saponite. Possible explanations for this different behaviour are discussed. The calculated isotropic chemical shift evolves progressively with the clay charge whereas the deduced quadrupolar interaction does not change significantly. The 27Al 2D 3QMAS technique was not able to resolve more than one signal.

The [AlO4/M+]0 (where M = H, Li, Na and K) defects in α-quartz have been investigated by ab initio calculations at the density functional theory (DFT) level, using the CRYSTAL06 code, 72-atom supercells, and all-electron basis sets. Our DFT calculations yielded substantially improved results than previous cluster calculations with minimal basis sets. For example, the [AlO4/M+(a<)]0 defects with M = H, Li and Na have been shown to be more stable than their [AlO4/M+(a>)]0 structural analogues (where a> and a< denote the location of the charge-compensating ion on the long-bond and short-bond side respectively), correctly predicting the common occurrence of paramagnetic [AlO4/M+(a>)]+ centres. In addition, the [AlO4/K+]0 defects have been investigated for the first time and are shown to be stable in quartz. Moreover, our calculations confirm previous suggestions that incorporation of the [AlO4/M+]0 defects results in significant structural relaxations that extend at least to the nearest Si atoms and give Li—O and Na—O bond distances in better agreement with the experimentally obtained values. The present theoretical results on the [AlO4/M+]0 defects provide a more complete picture for the coupled Al3+—M+ substitutions and hence new insights into crystal-chemical controls on the uptake of Al in quartz.

Understanding the precipitation of brittle hydride phases is crucial in establishing a failure criterion for various zirconium alloy nuclear fuel cladding. Accordingly, it is important to quantify the sensitivity of hydride precipitation to the component microstructure. This experimental investigation focuses on two microstructural characteristics and their role as hydride nucleation sites: The grain size and the alloy chemical composition. Samples of commercially pure zirconium (Zr-702) and Zircaloy-4, each with a wide range of grain sizes, were hydrided to 100 ppm and micrographs of the hydride distribution were optically analyzed for inter-granular and intra-granular precipitate sites. For most grain sizes, it was found that a significantly lower fraction of the precipitated hydrides nucleated at grain boundaries in Zircaloy-4 than in Zr-702, suggesting that a higher SPP content encourages the formation of intra-granular hydrides. Moreover, this effect became more prominent as the grain size increased; large-grain specimens contained a higher fraction of intra-granular hydrides than small-grain specimens of both Zr-702 and Zircaloy-4, highlighting the potency of grain boundaries as nucleation sites and how SPPs can influence the hydride distribution profile.

Polycrystalline materials’ mechanical properties and failure modes depend on many factors that include diffusion and segregation of different alloying elements and solutes as well as the structure of its grain boundaries (GBs). Segregated solute atoms to GB can alter the properties of steel alloys. Some of these elements lead to enhancing the strength of steel, on the other hand others can degrade the toughness of steel significantly. It is well known that carbon increases the cohesion at grain boundary. While the presence of hydrogen in steel have a drastic effects including blistering, flaking and embrittlement of steel. In practice during forming processes, the coincidence site lattice (CSL) GBs are experiencing deviations from their ideal configurations. Consequently, this will change the atomic structural integrity by superposition of sub-boundary dislocation networks on the ideal CSL interfaces. For this study, the ideal ∑3 (112) structure and its angular deviations in BCC iron within the range of Brandon criterion are studied comprehensively using molecular statics simulations. The GB and free surface segregation energies of carbon and hydrogen atoms will be quantified. Rice-Wang model is used to assess the strengthening/embrittlement impact variation over the deviation angles.

Understanding the ratcheting effect of hydrogen and hydride accumulation in response to thermal cycling is important in establishing a failure criterion for zirconium alloy nuclear fuel cladding. We propose a simple discrete dislocation plasticity model to study the evolution of the dislocation content that arises as a micro-hydride repeatedly precipitates and dissolves over a series of thermal cycles. With each progressive thermal cycle, we find a steady growth in the residual dislocation density in the vicinity of the hydride nucleation site; this corresponds to a gradual increase in the hydrogen concentration and, consequently, the hydride population. The simulated ratcheting in the dislocation density is consistent with experimental observations concerning the hysteresis in the terminal solid solubility of hydrogen in zirconium, which can be correlated to the plastic relaxation of hydrides.

Sustainable, carbon-free methods of large-scale hydrogen production are urgently needed to support industrial processes while decreasing carbon dioxide emissions. The realities of product development timelines dictate that existing commercial technologies such as low-temperature electrolysis will have to serve the majority of this need for at least the next 20 years. At the same time, even a cursory understanding of device design principles and real-world constraints can help to inform basic research. Accelerating the impact from fundamental material discoveries in related technologies therefore requires improved collaboration between academic, government, and industry sectors.

Renewable hydrogen is a key component to global decarbonization and reduction in carbon dioxide emissions. A common misconception is that the need for greener sources of hydrogen is dependent on whether fuel cell vehicles significantly penetrate the automotive market. However, hydrogen is a critical feedstock for many industrial processes, with an annual demand of 65 million metric tons globally. The large majority of this hydrogen is made via steam methane reforming, which represents the major carbon dioxide contribution for industrial processes such as ammonia production. Sustainable manufacturing of hydrocarbons also requires a sustainable source of hydrogen. Deep decarbonization and meeting 80% reduction targets for carbon dioxide emissions thus requires carbon-free sources of hydrogen. Based on the technology readiness levels, the reality is that existing commercial technologies will dominate the market for the next 20 years and beyond. To accelerate the impact of fundamental work in long-term technologies, improved collaboration between researchers across academic, government, and industry sectors is essential, to inform basic research as well as to leverage technology breakthroughs in the near term.

The present work investigates sol-gel synthesized vanadium oxyhydrate (V2O5·H2O) nanowires decorated with Au nanoparticles as potential photolytic H2 generators. As determined by UV photoelectron and optical spectroscopies, the conduction band edge of V2O5·H2O lies 0.6 eV below standard H+ reduction potential, implying no H2 can be generated. On the contrary, as measured by gas chromatography, our nanoconjugates yield reproducible light-to-hydrogen conversion efficiency of 5.3%, for the first hour of photolysis under 470 nm excitation. To explain the observed hydrogen reduction, we have hypothesized the vanadia electron energy levels are raised by some negative surface charge. With the objective of validating this hypothesis, we have performed cyclic current-voltage measurements. The derived conduction and valence band edge energies are not only consistent with the optical band gaps, but also validate the hypothesized energy increase by 1.6 eV, respectively. The negative surface charge is also corroborated by the ζ-potential. Based on the measured pH of 2.4, we attribute the negative surface charge to Lewis acid nature of the nanowires, establishing dative bonding with OH−. The present work establishes the importance of surface charge in photoelectrochemical reactions, where it can be instrumental and enabling in photolytic fuel production.

The hydrogen solubility and the vacancy concentration in Ni single crystals at thermal equilibrium with a H2 gas have been determined from a combination of first principles calculations and statistical mechanics up to the melting point. We show that the H solubility increases and the vacancy formation is promoted at high PH2. The apparent solution enthalpy and entropy are extracted from the fit of the solubility with the Sieverts’s law. We show that our results are in good agreement with previous experimental data at PH2=1 bar. The vacancy concentration increases with PH2 whatever the temperature but the effect of H is more significant at low temperature. However, the vacancy concentration and the H solubility in single crystals remain small and a comparison with the experimental data on polycrystals indicates that the grain boundaries may play the most important source of superabundant vacancies and preferential sites for H incorporation.

Semiconductor photocatalysis has emerged as an interesting area of research since the discovery of Honda-Fujishima effect. In this study, TiO2/MoO2/graphene composites have been prepared by a solar radiation-assisted co-reduction method, wherein ammonium tetrathiomolybdate salt and graphite oxide are reduced to MoO2 and graphene respectively along with TiO2. The method involved the utilization of focused pulses of natural sunlight using a simple convex lens, thereby eliminating the need for harmful reducing agents. The compound was characterized by XRD and SEM for phase identification and morphology. The TiO2/MoO2/graphene composite exhibits superior photocatalytic water splitting activity without using a co-catalyst. In addition, we demonstrate the electrocatalytic hydrogen production using this earth abundant catalyst, which shows high current density (60 mA/cm2) and low Tafel slope (47 mV/dec). The hydrogen evolved during photocatalysis was detected by gas chromatography.

A non-destructive neutron scattering method was developed to precisely measure the uptake of total hydrogen in nuclear grade Zircaloy-4 cladding. The hydriding apparatus consists of a closed stainless steel vessel that contains Zircaloy-4 specimens and hydrogen gas. By controlling the initial hydrogen gas pressure in the vessel and the temperature profile, target hydrogen concentrations from tens of ppm to a few thousands of ppm have been successfully achieved. Following hydrogen charging, the hydrogen content of the hydrided specimens was measured using the vacuum hot extraction method (VHE), by which the samples with desired hydrogen concentration were selected for the neutron study. Small angle incoherent neutron scattering (SAINS) were performed in the High Flux Isotope Reactor (HFIR) at Oak Ridge National Laboratory (ORNL). Our study indicates that a very small amount (≈ 20 ppm) hydrogen in commercial Zircaloy-4 cladding can be measured very accurately in minutes for a wide range of hydrogen concentration by a nondestructive method. The hydrogen distribution in a tube sample was obtained by scaling the neutron scattering rate with a factor, which is determined by calibration process with direct chemical analysis method on the specimen. This scale factor can be used for future test with unknown hydrogen concentration, thus provide a nondestructive method for absolute hydrogen concentration determination.

Pre-storage drying-transfer operations and early stage storage expose cladding to higher temperatures and much higher pressure-induced tensile hoop stresses relative to normal operation in-reactor and pool storage under these conditions. Radial hydrides precipitate during cooling and could provide an additional embrittlement mechanism as the cladding temperature decreases below the ductile-to-brittle transition temperature. To simulate this behavior, unirradiated Zircaloy-4 samples were hydrided by a gas charging method to levels that encompass the range of hydrogen concentrations observed in current used fuel. Mechanical testing was carried out by the ring compression test (RCT) method at various temperatures to evaluate the sample’s ductility for both as-hydrided and post-hydride reorientation treated specimens. As-hydrided samples with higher hydrogen concentration (>800 ppm) resulted in lower strain before fracture and reduced maximum load. Increasing RCT temperatures resulted in increased ductility of the as-hydrided cladding. A systematic radial hydride treatment was conducted at various pressures and temperatures for the hydrided samples with H content around 200 ppm. Following the radial hydride treatment, RCTs on the hydride reoriented samples were conducted and exhibited lower ductility compared to as-hydrided samples.

Homogenous strontium titanate (SrTiO3) nanofibers were prepared via the electrospinning of precursor solutions containing both strontium and titanium salts. Photocatalytic activities of these SrTiO3 nanofibers for hydrogen generation from water were examined and compared to that of SrTiO3 nanoparticles. The nanofibers calcined at 700 °C showed the highest photocatalytic activity of 167 μmol/h/g among the SrTiO3 samples tested. The high activity was attributed to the ideal stoichiometric ratio of Ti/Sr, small crystallite size, high crystallinity, mesoporous structure, large surface area, and appropriate energy gap. These were confirmed through field emission scanning electron microscopic with energy dispersive spectroscopic observations, x-ray diffraction patterns, N2 gas absorption–desorption isotherm measurements, photoelectron yield spectroscopy in air, and UV-visible spectrophotometry.

Aluminum hydride (AlH3), and the complex aluminum hydrides (e.g., M3AlH6, MAlH5, M2AlH7, M(AlH4)n), make up a fascinating class of materials that have received considerable attention over the past 60 years for their use as explosives, reducing agents, solid rocket propellants, as well as a hydrogen source for portable power systems. The recent renaissance in hydrogen storage research, particularly for automotive applications, has generated renewed interest in aluminum-based hydrides due to their capacity to store up to 11 wt% hydrogen with volumetric capacities up to 150 g H2/L (more than twice that of liquid hydrogen). In addition, hydrogen can be released from these materials by low temperature thermolysis (<100°C), making them well-suited for proton exchange membrane fuel cells and other low temperature applications. This article covers recent research on aluminum-based hydrides, including crystal structures, thermodynamics, kinetics, hydrogenation conditions, and regeneration methods.

Hydrogen can be used as an environmentally friendly fuel to power vehicles, electric devices, and spacecraft with water vapor as the only emission. One associated challenge is the development of safe hydrogen storage systems. Hydrogen tanks and other hydrogen infrastructure elements will be exposed to both high-pressure hydrogen and cyclic stresses. In our work, 304 stainless steel specimens were precharged with hydrogen and subjected to rotational bending fatigue with a maximum stress amplitude of 90 ksi. A diffusion model was solved to approximate the concentration of hydrogen in the specimen at the time of the test. Contrary to our previous work with simple bending fatigue tests, hydrogen precharging actually increased rotational bending fatigue life from 28,074 (Sx = 7,430, N = 103) cycles to 91,513 (Sx = 40,209, N=32) cycles, a factor of approximately 3.25. This result demonstrates that the effect of hydrogen on fatigue life can be highly situational, and great care should be taken when designing systems that will be exposed to high-pressure hydrogen under fatigue conditions.

Energy storage is a key technology for establishing a stand-alone renewable energy system. Current energy-storage technologies are, however, not suitable for such an energy system. They are cost ineffective and/or are with low energy-conversion efficiency. Hydrogen generation and storage from water by sunlight is one of these technologies. In this study, a simple concept of hydrogen generation from water by using sunlight, “concentrated photovoltaic electrochemical cell (CPEC)” is proposed. It is experimentally shown that the CPEC operates stably and achieves conversion efficiency from light to hydrogen energy of over 12%.

Density functional theory calculations are used to address the energetics of protons crossing “triple phase boundaries” based on Pd and barium zirconate. Our calculations show that the proton transfer reaction at these triple phase boundaries is controlled by the terminal layer of the electrolyte in contact with the metallic catalyst and gas phase. Hydrogen spilling onto the electrolyte surface is energetically favored at peripherical sites of the metal-electrolyte interface, and proton incorporation into the sub-surface region of the electrolyte involves energies of the order of 1 eV. At the triple phase boundary, the energy cost associated with the proton transfer reaction is controlled by both the nature of chemical contact and the Schottky barrier at the metal-electrolyte interface.

Plutonium and Pu-Ga alloys have been observed to have anomalous hydrogen solubility behavior, including a significant concentration dependence of hydrogen diffusivity in the dilute regime, a sharp drop off in the hydrogen solubility constant in the dilute regime, and a near complete absence of change in the Sieverts’ constant as the alloys are heated across phase transformation boundaries. We are investigating the possibility that a vacancy mechanism is responsible for this behavior. X-ray diffraction measurements show a 0.14% lattice contraction in Pu-2 at. % Ga alloys when they are charged with ~2 at. % hydrogen. The lattice re-expands when the hydrogen is removed. Density functional calculations show that increasing the number of hydrogen atoms associated with a vacant lattice site in Pu lowers the energy of the hydrogen-vacancy complex. These observations support the idea that vacancies are stabilized by hydrogen in the Pu lattice well beyond their thermal equilibrium concentration and could be responsible for the anomalous hydrogen response of Pu.

Hydrogen blister rates in Si (100), Si (111) and Ge (100) substrates are compared as a function of annealing temperature and time, for a range of implant energies and fluences. For each material, the rate of blister formation was found to exhibit Arrhenius behavior and to be characterised by a single activation energy over the temperature range examined. The extracted activation energies were 2.28±0.03 eV, 2.17±0.06 eV and 1.4±0.03 eV for (100) Si; (111) Si and (100) Ge, respectively. These results are compared with reported measurements and discussed in relation to proposed models of hydrogen blistering.

Hydrogenated polymorphous silicon (pm-Si:H) is one of the most promising candidates for a stable top cell material in multi-junction thin film solar cells. Solar cells using pm-Si:H as their absorbing layer show very interesting degradation kinetics when compared to hydrogenated amorphous silicon (a-Si:H), summarized by macroscopic structural changes and irreversible changes in solar cell characteristics, while nevertheless preserving a higher stabilized efficiency. Notably, pm-Si:H solar cells, once degraded, respond to neither annealing nor further light-soaking. Such results suggest a device degradation mechanism including structural changes, active hydrogen motion, and interface delamination mediated by fast hydrogen diffusion and accumulation at the interface. Interestingly, a similar behavior was reported for a-Si:H solar cells under severe light soaking conditions (at 350 °C or under 50 suns) while pm-Si:H solar cells show such behavior under 1 sun at 40 °C.

We confirmed that GaN photocatalyst with NiO cocatalyst (GaN-NiO) continuously produced hydrogen from water for 500 hours without any extra bias. The GaN-NiO photocatalyst was hardly etched and 184-mL hydrogen gas was produced from the electric charge of 1612 coulombs, the Faradic efficiency of which was 89.2%. The conversion efficiency from incident light energy to hydrogen chemical energy was 0.98% in average for 500 h. The incident photon-to-current conversion efficiency (IPCE) was 50% at 300 nm and 35% at 350 nm after the experiment, which was much higher than those of other semiconductor-based photocatalysts.