In this paper, we investigate by ab initio DFT how the O:H ratio influences the formation and lattice energy, metastability, and optical properties of Y and La anion-disordered ROxH3-2x oxyhydrides. To achieve this, a set of special quasirandom structures (SQS) is introduced to model anion-disorder along the whole RH3-R2O3 composition line. A comparison with an extensive set of anion-ordered polymorphs of the same composition shows the comparable energy of the anion-disordered phase, which, in particular, in the H-rich composition interval showed the lowest relative energy. In turn, the metastability of the anion-disordered phase depends on the cation size (Y versus La), which determines the maximum H content above which the CaF2-type structure itself becomes unstable. To overcome the accuracy limitations of classical DFT, the modified Becke-Johnson (mBJ) scheme is employed in the study of the electronic properties. We show that major differences occur between H-rich and O-rich R oxyhydrides, as the octahedral H- present for x<1 form electronic states at the top of the valence band, which reduce the energy band gap and dominate the electronic transitions at lower energies, thus increasing the refractive index of the material in the VIS-nIR spectral range. Comparing the DFT results to experimental data on photochromic Y oxyhydride films reinforces the hypothesis of anion-disorder in the H-rich films (x<1), while it hints towards some degree of anion ordering in the O-rich ones (x>1). Our paper exemplifies a strategy to calculate ab initio the electronic/optical properties of a wide range of materials with occupational disorder.@en

Rare earth oxyhydrides REOxH(3-2x), with RE = Y, Sc, or Gd and a cationic FCC lattice, are reversibly photochromic in nature. It is known that structural details and anion (O2-:H-) composition dictate the efficiency of the photochromic behavior. The mechanism behind the photochromism is, however, not yet understood. In this study, we use 1H, 2H, 17O, and 89Y solid-state NMR spectroscopy and density functional theory (DFT) calculations to study the various yttrium, hydrogen, and oxygen local environments, anion oxidation states, and hydride ion dynamics. DFT models of YOxH(3-2x) with both anion-ordered and anion-disordered sublattices are constructed for a range of compositions and show a good correlation with the experimental NMR parameters. Two-dimensional 17O-1H and 89Y-1H NMR correlation experiments reveal heterogeneities in the samples, which appear to consist of hydride-rich (x ≈ 0.25) and hydride-poor domains (x ≈ 1) rather than a single composition with homogeneous anion mixing. The compositional variation (as indicated by the different x values in YOxH(3-2x)) is determined by comparing static 1H NMR line widths with calculated 1H-1H dipolar couplings of yttrium oxyhydride models. The 1D 17O MAS spectrum demonstrates the presence of a small percentage of hydroxide (OH-) ions. DFT modeling indicates a reaction between the protons of hydroxides and hydrides to form molecular hydrogen (H+ + H- → H2). 1H MAS NMR indicates the presence of a mobile component that, based on this finding, is attributed to trapped molecular H2 in the lattice.@en

One of the main challenges of all-solid-state Li-ion batteries is the restricted power density due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion conductivity, using a combination of 7Li NMR experiments and DFT based molecular dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange experiments are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quantitative insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.@en

Rare-Earth oxyhydrides (REH3-2xOx) are characterized by photodarkening when illuminated by photons having an energy exceeding that of the band gap. We propose that the film is segregated in hydrogen rich and hydrogen poor areas. Upon illumination, the excited electrons reduce the three-valent cations inducing an insulator to metal transition in the hydrogen rich entities. These small metallic oxyhydride clusters are responsible for the enhanced optical absorption. In the surrounding semiconductor matrix the photoexcitation induces a transition from p to n-type conductivity. This persistent photoconductivity is due to trapping of the holes by hydride ions. As a result, the Fermi level rises above the conduction band inducing a Burstein-Moss effect and a large increase in the conductivity.@en

Rare-Earth oxyhydrides (REH3-2xOx) are characterized by photodarkening when illuminated by photons having an energy exceeding that of the band gap. We propose that the film is segregated in hydrogen rich and hydrogen poor areas. Upon illumination, the excited electrons reduce the three-valent cations inducing an insulator to metal transition in the hydrogen rich entities. These small metallic oxyhydride clusters are responsible for the enhanced optical absorption. In the surrounding semiconductor matrix the photoexcitation induces a transition from p to n-type conductivity. This persistent photoconductivity is due to trapping of the holes by hydride ions. As a result, the Fermi level rises above the conduction band inducing a Burstein-Moss effect and a large increase in the conductivity.@en

Rare-Earth oxyhydrides (REH3-2xOx) are characterized by photodarkening when illuminated by photons having an energy exceeding that of the band gap. We propose that the film is segregated in hydrogen rich and hydrogen poor areas. Upon illumination, the excited electrons reduce the three-valent cations inducing an insulator to metal transition in the hydrogen rich entities. These small metallic oxyhydride clusters are responsible for the enhanced optical absorption. In the surrounding semiconductor matrix the photoexcitation induces a transition from p to n-type conductivity. This persistent photoconductivity is due to trapping of the holes by hydride ions. As a result, the Fermi level rises above the conduction band inducing a Burstein-Moss effect and a large increase in the conductivity.@en

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.@en

A novel route to prepare highly active and stable N2O decomposition catalysts is presented, based on Fe-exchanged beta zeolite. The procedure consists of liquid phase Fe(III) exchange at low pH. By varying the pH systematically from 3.5 to 0, using nitric acid during each Fe(III)-exchange procedure, the degree of dealumination was controlled, verified by ICP and NMR. Dealumination changes the presence of neighbouring octahedral Al sites of the Fe sites, improving the performance for this reaction. The so-obtained catalysts exhibit a remarkable enhancement in activity, for an optimal pH of 1. Further optimization by increasing the Fe content is possible. The optimal formulation showed good conversion levels, comparable to a benchmark Fe-ferrierite catalyst. The catalyst stability under tail gas conditions containing NO, O2 and H2O was excellent, without any appreciable activity decay during 70 h time on stream. Based on characterisation and data analysis from ICP, single pulse excitation NMR, MQ MAS NMR, N2 physisorption, TPR(H2) analysis and apparent activation energies, the improved catalytic performance is attributed to an increased concentration of active sites. Temperature programmed reduction experiments reveal significant changes in the Fe(III) reducibility pattern with the presence of two reduction peaks; tentatively attributed to the interaction of the Fe-oxo species with electron withdrawing extraframework AlO6 species, causing a delayed reduction. A low-temperature peak is attributed to Fe-species exchanged on zeolitic AlO4 sites, which are partially charged by the presence of the neighbouring extraframework AlO6 sites. Improved mass transport phenomena due to acid leaching is ruled out. The increased activity is rationalized by an active site model, whose concentration increases by selectively washing out the distorted extraframework AlO6 species under acidic (optimal) conditions, liberating active Fe species.@en

Osteoporosis is the most widespread metabolic bone disease which represents a major public health burden. Consequently, novel biomaterials with a strong capacity to regenerate osteoporotic bone defects are urgently required. In view of the anti-osteoporotic and osteopromotive efficacy of alendronate and 45S5 bioactive glass, respectively, we investigated the feasibility to synthesize novel hybrid particles by exploiting the strong interactions between these two compounds. Herein, we demonstrate the facile preparation of a novel class of hybrid particles of tunable morphology, chemical composition and structure. These hybrid particles (i) release alendronate and various inorganic elements (Ca, Na, Si, and P) in a controlled manner, (ii) exhibit a strong anti-osteoclastic effect in vitro, and (iii) stimulate regeneration of osteoporotic bone in vivo. Consequently, this novel class of hybrid biomaterials opens up new avenues of research on the design of bone substitutes with specific activity to facilitate regeneration of bone defects in osteoporotic patients.@en

Amorphous titanium oxide nanoparticles were prepared from titanium isopropoxide. In situ measurements reveal an extraordinary high capacity of 810 mAh/g on the first discharge. Upon cycling at a charge/discharge rate of 33.5 mA/g, this capacity gradually decreases to 200 mAh/g after 50 cycles. The origin of this fading was investigated using X-ray absorption spectroscopy and solid-state nuclear magnetic resonance. These measurements reveal that a large fraction of the total amount of the consumed Li atoms is due to the reaction of H2 O/OH species adsorbed at the surface to Li2 O, explaining the irreversible capacity loss. The reversible capacity of the bulk, leading to the Li0.5 TiO2 composition, does not explain the relatively large reversible capacity, implying that part of Li2 O at the TiO2 surface may be reversible. The high reversible capacity, also at large (dis)charge rates up to 3.35 A/g (10C), makes this amorphous titanium oxide material suitable as a low cost electrode material in a high power battery.@en

Amorphous titanium oxide nanoparticles were prepared from titanium isopropoxide. In situ measurements reveal an extraordinary high capacity of 810 mAh/g on the first discharge. Upon cycling at a charge/discharge rate of 33.5 mA/g, this capacity gradually decreases to 200 mAh/g after 50 cycles. The origin of this fading was investigated using X-ray absorption spectroscopy and solid-state nuclear magnetic resonance. These measurements reveal that a large fraction of the total amount of the consumed Li atoms is due to the reaction of H2 O/OH species adsorbed at the surface to Li2 O, explaining the irreversible capacity loss. The reversible capacity of the bulk, leading to the Li0.5 TiO2 composition, does not explain the relatively large reversible capacity, implying that part of Li2 O at the TiO2 surface may be reversible. The high reversible capacity, also at large (dis)charge rates up to 3.35 A/g (10C), makes this amorphous titanium oxide material suitable as a low cost electrode material in a high power battery.@en

Amorphous titanium oxide nanoparticles were prepared from titanium isopropoxide. In situ measurements reveal an extraordinary high capacity of 810 mAh/g on the first discharge. Upon cycling at a charge/discharge rate of 33.5 mA/g, this capacity gradually decreases to 200 mAh/g after 50 cycles. The origin of this fading was investigated using X-ray absorption spectroscopy and solid-state nuclear magnetic resonance. These measurements reveal that a large fraction of the total amount of the consumed Li atoms is due to the reaction of H2 O/OH species adsorbed at the surface to Li2 O, explaining the irreversible capacity loss. The reversible capacity of the bulk, leading to the Li0.5 TiO2 composition, does not explain the relatively large reversible capacity, implying that part of Li2 O at the TiO2 surface may be reversible. The high reversible capacity, also at large (dis)charge rates up to 3.35 A/g (10C), makes this amorphous titanium oxide material suitable as a low cost electrode material in a high power battery.@en

The microstructure of several YBa2Cu3O7-x superconducting thin films has been investigated by transmission electron microscopy. Films, with a thickness ranging from 250 to 500 nm, were grown by triode sputtering on (001) SrTiO3. The films are amorphous upon deposition. After annealing in oxygen, epitaxial grains are found. Depending on the annealing conditions, a high density of twin boundaries was observed. X-ray diffraction shows that the orientation of the majority of the grains changes with film thickness. In the thinner films (250 nm) the c axis is preferentially oriented perpendicular to the substrate. In thicker films a preferential a orientation is observed. High-resolution electron microscopy (HREM) reveals that both types of films show an initial growth with the c axis perpendicular to the substrate. Films with a thickness in excess of 500 nm also showed the presence of randomly oriented grains with no orientational relationship to the substrate. It is concluded that the nucleation process at the substrate-film interface is not determined by the lattice match, but rather by the favorable interaction of one kind of the YBa2Cu3O7-x metal-oxide layers with the substrate surface.@en