Idoia Ruiz de Larramendi

Antibacterial properties of nanoparticles

Antibacterial agents are very important in the textile industry, water disinfection, medicine, and food packaging. Organic compounds used for disinfection have some disadvantages, including toxicity to the human body, therefore, the interest in inorganic disinfectants such as metal oxide nanoparticles (NPs) is increasing. This review focuses on the properties and applications of inorganic nanostructured materials and their surface modifications, with good antimicrobial activity. Such improved antibacterial agents locally destroy bacteria, without being toxic to the surrounding tissue. We also provide an overview of opportunities and risks of using NPs as antibacterial agents. In particular, we discuss the role of different NP materials.

In vivo integrity of polymer-coated gold nanoparticles

Inorganic nanoparticles are frequently engineered with an organic surface coating to improve their physicochemical properties, and it is well known that their colloidal properties may change upon internalization by cells. While the stability of such nanoparticles is typically assayed in simple in vitro tests, their stability in a mammalian organism remains unknown. Here, we show that firmly grafted polymer shells around gold nanoparticles may degrade when injected into rats. We synthesized monodisperse radioactively labelled gold nanoparticles ((198)Au) and engineered an (111)In-labelled polymer shell around them. Upon intravenous injection into rats, quantitative biodistribution analyses performed independently for (198)Au and (111)In showed partial removal of the polymer shell in vivo. While (198)Au accumulates mostly in the liver, part of the (111)In shows a non-particulate biodistribution similar to intravenous injection of chelated (111)In. Further in vitro studies suggest that degradation of the polymer shell is caused by proteolytic enzymes in the liver. Our results show that even nanoparticles with high colloidal stability can change their physicochemical properties in vivo.

Sodium–Oxygen Battery: Steps Toward Reality

Rechargeable metal-oxygen batteries are receiving significant interest as a possible alternative to current state of the art lithium ion batteries due to their potential to provide higher gravimetric energies, giving significantly lighter or longer-lasting batteries. Recent advances suggest that the Na-O2 battery, in many ways analogous to Li-O2 yet based on the reversible formation of sodium superoxide (NaO2), has many advantages such as a low charge overpotential (∼100 mV) resulting in improved efficiency. In this Perspective, we discuss the current state of knowledge in Na-O2 battery technology, with an emphasis on the latest experimental studies, as well as theoretical models. We offer special focus on the principle outstanding challenges and issues and address the advantages/disadvantages of the technology when compared with Li-O2 batteries as well as other state-of-the-art battery technologies. We finish by detailing the direction required to make Na-O2 batteries both commercially and technologically viable.

New Insights into the Instability of Discharge Products in Na-O2 Batteries.

Sodium-oxygen batteries currently stimulate extensive research due to their high theoretical energy density and improved operational stability when compared to lithium-oxygen batteries. Cell stability, however, needs to be demonstrated also under resting conditions before future implementation of these batteries. In this work we analyze the effect of resting periods on the stability of the sodium superoxide (NaO2) discharge product. The instability of NaO2 in the cell environment is demonstrated leading to the evolution of oxygen during the resting period and the decrease of the cell efficiency. In addition, migration of the superoxide anion (O2(-)) in the electrolyte is observed and demonstrated to be an important factor affecting Coulombic efficiency.

Carbon-Free Cathodes: A Step Forward in the Development of Stable Lithium-Oxygen Batteries.

Lithium-oxygen (Li-O2 ) batteries are receiving considerable interest owing to their potential for higher energy densities than current Li-ion systems. However, the lack stability of carbon-based oxygen electrodes is believed to promote carbonate formation leading to capacity fade and limiting the cycling performance of the battery. To improve the stability and cyclability of these systems, alternative electrode materials are required. Metal oxides are mainly utilized at low current densities, whereas noble metals show outstanding performance at high current densities. Carbides appear to provide a good compromise between electrochemical performance and cost, which makes them interesting materials for further investigations. Here, a critical review of current carbon-free electrode research is provided with the goal of identifying routes to its successful optimization.

A novel one step synthesized Co-free perovskite/brownmillerite nanocomposite for solid oxide fuel cells

Cobalt-free perovskite oxides Pr1−xCaxFe0.8Ni0.2O3 (PCFN) were investigated as novel cathodes for intermediate temperature solid oxide fuel cells (IT-SOFCs). Ca and Ni substitution in the PrFeO3 material shows that a wide range of perovskites Pr1−xCaxFe0.8Ni0.2O3 (0 < x < 0.9) can be prepared by sintering in air at 600 °C. Perovskites with 0 < x < 0.4 exhibit orthorhombic single phases (Pnma space group), whereas 0.4 < x < 0.9 show a coexistence of the perovskite and the brownmillerite-type structure (Ca2Fe2O5). The structure of the polycrystalline powders was analyzed by X-ray powder diffraction, Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The analysis on the synthesized powders shows the presence of clusters formed by 30–100 nm nanoparticles. High-Resolution TEM (HRTEM) studies were carried out to confirm the existence of Ca2Fe2O5. The dc four-probe measurement exhibits a total electrical conductivity, over 100 S cm−1 at T ≥ 600 °C when 0 < x < 0.6, pointing out that strontium can be substituted for calcium without modifying the electrochemical properties. The Pr0.4Ca0.6Fe0.8Ni0.2O3/Ca2Fe2O5 composite cathode presents the better performance in electrochemical measurements, showing an area specific resistance value of 0.09 ohm cm2 at 850 °C.

A straightforward synthesis of carbon nanotube–perovskite composites for solid oxide fuel cells

A powerful non-difficult and economical route based on the addition of carbon nanotubes (CNTs) is presented for the synthesis of nanostructured materials. For the first time, CNTs have been used as composite materials with a perovskite-type oxide for SOFC devices giving rise to an improved electrochemical behavior at intermediate temperatures.

A New Partially Deprotonated Mixed-Valence Manganese(II,III) Hydroxide–Arsenate with Electronic Conductivity: Magnetic Properties of High- and Room-Temperature Sarkinite

A new three-dimensional hydroxide-arsenate compound called compound 2 has been synthesized by heating (in air) of the sarkinite phase, Mn(2)(OH)AsO(4) (compound 1), with temperature and time control. The crystal structure of this high-temperature compound has been solved by Patterson-function direct methods. A relevant feature of this new material is that it is actually the first member of the adamite-type family with mixed-valence manganese(II,III) and electronic conductivity. Crystal data: a = 6.7367(5) Å, b = 7.5220(6) Å, c = 9.8117(6) Å, α = 92.410(4)°, β = 109.840(4)°, γ = 115.946(4)°, P1̅. The unit cell content derived from Rietveld refinement is Mn(8)(O(4)H(x))(AsO(4))(4). Its framework, projected along [111], is characterized by rings of eight Mn atoms with the OH(-)/O(2-) inside the rings. These rings form an almost perfect hexagonal arrangement with the AsO(4) groups placed in between. Bond-valence analysis indicates both partial deprotonation (x ≅ 3) and the presence of Mn in two different oxidation states (II and III), which is consistent with the electronic conductivity above 300 °C from electrochemical measurements. The electron paramagnetic resonance spectra of compound 1 and of its high-temperature form compound 2 show the presence of antiferromagnetic interactions with stronger magnetic coupling for the high-temperature phase. Magnetization measurements of room-temperature compound 1 show a complex magnetic behavior, with a three-dimensional antiferromagnetic ordering and magnetic anomalies at low temperatures, whereas for compound 2, an ordered state is not reached. Magnetostructural correlations indicate that superexchange interactions via oxygen are present in both compounds. The values of the magnetic exchange pathways [Mn-O-Mn] are characteristic of antiferromagnetic couplings. Notwithstanding, the existence of competition between different magnetic interactions through superexchange pathways can cause the complex magnetic behavior of compound 1. The loss of three-dimensional magnetic ordering by heating of compound 1 could well be based on the presence of Mn(3+) ions (d(4)) in compound 2.

Effect of Electrolyte Contribution on the Electrochemical Behaviour of Pr0.8Sr0.2Fe0.8Ga0.2O3

Pr0.8Sr0.2Fe0.8Ga0.2O3 (PSFG) phase with perovskite-type structure was obtained by a glycine nitrate process. The product was characterized by X-ray diffraction and an orthorhombic structure (Pbnm) was found. The study of morphology indicates the existence of inhomogeneous particle size and agglomerates. The polarization resistance was studied using different electrolytes: Yttrium-stabilized zirconia (YSZ); Samarium-doped ceria (SDC); Praseodymium-doped ceria (CPO) and Gadolinium-doped ceria (CGO). No chemical reactivity between the PSFG and the electrolytes was observed. Electrochemical Impedance Spectroscopy measurements of PSFG/electrolyte/PSFG test cells were carried out. These electrochemical experiments were performed at equilibrium from 850oC to room temperature, under both zero dc current intensity and air. The obtained ASR values at 850oC for the cell tests were: 0.67 Ω·cm (YSZ); 0.55 Ω·cm (SDC); 0.26 Ω·cm (CPO) and 0.68 Ω·cm (CGO).

Exploring Reaction Conditions to Improve the Magnetic Response of Cobalt-Doped Ferrite Nanoparticles

With the aim of studying the influence of synthesis parameters in structural and magnetic properties of cobalt-doped magnetite nanoparticles, Fe3−xCoxO4 (0 < x < 0.15) samples were synthetized by thermal decomposition method at different reaction times (30–120 min). The Co ferrite nanoparticles are monodisperse with diameters between 6 and 11 nm and morphologies depending on reaction times, varying from spheric, cuboctahedral, to cubic. Chemical analysis and X-ray diffraction were used to confirm the composition, high crystallinity, and pure-phase structure. The investigation of the magnetic properties, both magnetization and electronic magnetic resonance, has led the conditions to improve the magnetic response of doped nanoparticles. Magnetization values of 86 emu·g−1 at room temperature (R.T.) have been obtained for the sample with the highest Co content and the highest reflux time. Magnetic characterization also displays a dependence of the magnetic anisotropy constant with the varying cobalt content.