Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Structural Aspects of P2-Type Na0.67Mn0.6Ni0.2Li0.2O2 (MNL) Stabilization by Lithium Defects as a Cathode Material for Sodium-Ion Batteries

A known strategy for improving the properties of layered oxide electrodes in sodium-ion batteries is the partial substitution of transition metals by Li. Herein, the role of Li as a defect and its impact on sodium storage in P2-Na_0.67Mn_0.6Ni_0.2Li_0.2O₂ is discussed. In tandem with electrochemical studies, the electronic and atomic structure are studied using solid-state NMR, operando XRD, and density functional theory (DFT). For the as-synthesized material, Li is located in comparable amounts within the sodium and the transition metal oxide (TMO) layers. Desodiation leads to a redistribution of Li ions within the crystal lattice. During charging, Li ions from the Na layer first migrate to the TMO layer before reversing their course at low Na contents. There is little change in the lattice parameters during charging/discharging, indicating stabilization of the P2 structure. This leads to a solid-solution type storage mechanism (sloping voltage profile) and hence excellent cycle life with a capacity of 110 mAh g^-1 after 100 cycles. In contrast, the Li-free compositions Na_0.67Mn_0.6Ni_0.4O₂ and Na_0.67Mn_0.8Ni_0.2O₂ show phase transitions and a stair-case voltage profile. The capacity is found to originate from mainly Ni³⁺/Ni⁴⁺ and O^2-/O^2-δ redox processes by DFT, although a small contribution from Mn⁴⁺/Mn⁵⁺ to the capacity cannot be excluded.     

Current advances concerning the most cited metal ions doped bioceramics and silicate-based bioactive glasses for bone tissue engineering

Studies related to biomaterials that stimulate the repair of living tissue have increased considerably, improving the quality of many people's lives that require surgery due to traumatic accidents, bone diseases, bone defects, and reconstructions. Among these biomaterials, bioceramics and bioactive glasses (BGs) have proved to be suitable for coating materials, cement, scaffolds, and nanoparticles, once they present good biocompatibility and degradability, able to generate osteoconduction on the surrounding tissue. However, the role of biomaterials in hard tissue engineering is not restricted to a structural replacement or for guiding tissue regeneration. Nowadays, it is expected that biomaterials develop a multifunctional role when implanted, orchestrating the process of tissue regeneration and providing to the body the capacity to heal itself. In this way, the incorporation of specific metal ions in bioceramics and BGs structure, including magnesium, silver, strontium, lithium, copper, iron, zinc, cobalt, and manganese are currently receiving enhanced interest as biomaterials for biomedical applications. When an ion is incorporated into the bioceramic structure, a new category of material is created, which has several unique properties that overcome the disadvantages of primitive material and favors its use in different biomedical applications. The doping can enhance handling properties, angiogenic and osteogenic performance, and antimicrobial activity. Therefore, this review aims to summarize the effect of selected metal ion dopants into bioceramics and silicate-based BGs in bone tissue engineering. Furthermore, new applications for doped bioceramics and BGs are highlighted, including cancer treatment and drug delivery.     

Blends of Bio-Based Poly(Limonene Carbonate) with Commodity Polymers

In this study, blends of the bio-based poly(limonene carbonate) (PLimC) with different commodity polymers are investigated in order to explore the potential of PLimC toward generating more sustainable polymer materials by reducing the amount of petro- or food-based polymers. PLimC is employed as minority component in the blends. Next to the morphology and thermal properties of the blends the impact of PLimC on the mechanical properties of the matrix polymers is studied. The interplay of incompatibility and zero-shear melt viscosity contrast determines the blend morphology, leading for all blends to a dispersed droplet morphology for PLimC. Blends with polymers of similar structure to PLimC (i.e., aliphatic/aromatic polyester) show the best performance with respect to mechanical properties, whereas blends with polystyrene or poly(methyl methacrylate) are too brittle and polyamide 12 blends show very low elongations at break. In blends with Ecoflex (poly(butylene adipate-co-terephthalate)) and Arnitel EM400 (copoly(ether ester)) with poly(butylene terephthalate) hard and polytetrahydrofuran soft segments) a threefold increase in E-modulus can be achieved, while keeping the elongation at break at reasonable high values of ≈200%, making these blends highly interesting for applications.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

Revealing Electrical-Poling-Induced Polarization Potential in Hybrid Perovskite Photodetectors

Despite recent rapid advances in metal halide perovskites for use in optoelectronics, the fundamental understanding of the electrical-poling-induced ion migration, accounting for many unusual attributes and thus performance in perovskite-based devices, remain comparatively elusive. Herein, the electrical-poling-promoted polarization potential is reported for rendering hybrid organic–inorganic perovskite photodetectors with high photocurrent and fast response time, displaying a tenfold enhancement in the photocurrent and a twofold decrease in the response time after an external electric field poling. First, a robust meniscus-assisted solution-printing strategy is employed to facilitate the oriented perovskite crystals over a large area. Subsequently, the electrical poling invokes the ion migration within perovskite crystals, thus inducing a polarization potential, as substantiated by the surface potential change assessed by Kelvin probe force microscopy. Such electrical-poling-induced polarization potential is responsible for the markedly enhanced photocurrent and largely shortened response time. This work presents new insights into the electrical-poling-triggered ion migration and, in turn, polarization potential as well as into the implication of the latter for optoelectronic devices with greater performance. As such, the utilization of ion-migration-produced polarization potential may represent an important endeavor toward a wide range of high-performance perovskite-based photodetectors, solar cells, transistors, scintillators, etc.     

High-resolution FIB-TEM-STEM structural characterization of grain boundaries in the high dielectric constant perovskite CaCu3Ti4O12

In this work, the grain boundaries composition of the polycrystalline CaCu₃Ti₄O₁₂ (CCTO) was investigated. A Focused Ion Beam (FIB)/lift-out technique was used to prepare site-specific thin samples of the grain boundaries interface of CCTO ceramics. Scanning transmission electron microscopy (STEM) coupled with energy dispersive X-ray spectrometry (EDXS) and Electron Energy Loss Spectroscopy (EELS) systems were used to characterize the composition and nanostructure of the grain and grain boundaries region. It is known that during conventional sintering, discontinuous grain growth occurs and a Cu-rich phase appears at grain boundaries. This Cu-rich phase may affect the final dielectric properties of CCTO but its structure and chemical composition remained unknown. For the first time, this high-resolution FIB-TEM-STEM study of CCTO interfacial region highlights the composition of the phases segregated at grain boundaries namely CuO, Cu₂O and the metastable phase Cu₃TiO_4.