Microwave-assisted synthesis and electrochemical evaluation of VO2 (B) nanostructures

Understanding how intercalation materials change during electrochemical operation is paramount to optimizing their behaviour and function and in situ characterization methods allow us to observe these changes without sample destruction. Here we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave-assisted route which exhibits a larger electrochemical capacity (232 mAh g-1) compared with VO2 (B) prepared by a solvothermal route (197 mAh g-1). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during battery operation

One pot solvothermal synthesis of organic acid coated magnetic iron oxide nanoparticles

Indexación: ScieloABSTRACT In this work we present the synthesis and characterization of iron oxide nanoparticles (IONPs), which were structurally and magnetically characterized. The use of iron salts and an organic acid (l-serine or ascorbic acid) as precursors under solvothermal conditions yielded these coated IONPs. The powder X-ray diffraction pattern of FeO-1 and FeO-2 is consistent with hematite (α-Fe2O3) and hematite-maghemite ((α-Fe2O3/γ-Fe2O3) respectively. The TEM analysis permits to estimate an average size of 10 nm for the FeO-1 sample. The magnetic characterization of the samples through the M(H) plots showed a very low coercivity value for both samples, being 53 Oe for FeO-1 and 10 Oe for FeO-2, indicating the very weak ferromagnetic character of the synthesized iron oxide species. Even though both organic acids under solvothermal conditions permit to obtain coated IONPs in one pot reaction, l-serine produces a more narrow-size distribution

Structure–property insights into nanostructured electrodes for Li-ion batteries from local structural and diffusional probes

Microwave heating presents a faster, lower energy synthetic methodology for the realization of functional materials. Here, we demonstrate for the first time that employing this method also leads to a decrease in the occurrence of defects in olivine structured LiFe1−xMnxPO4. For example, the presence of antisite defects in this structure precludes Li+ diffusion along the b-axis leading to a significant decrease in reversible capacities. Total scattering measurements, in combination with Li+ diffusion studies using muon spin relaxation (μ+SR) spectroscopy, reveal that this synthetic method generates fewer defects in the nanostructures compared to traditional solvothermal routes. Our interest in developing these routes to mixed-metal phosphate LiFe1−xMnxPO4 olivines is due to the higher Mn2+/3+ redox potential in comparison to the Fe2+/3+ pair. Here, single-phase LiFe1−xMnxPO4 (x = 0, 0.25, 0.5, 0.75 and 1) olivines have been prepared following a microwave-assisted approach which allows for up to 4 times faster reaction times compared to traditional solvothermal methods. Interestingly, the resulting particle morphology is dependent on the Mn content. We also examine their electrochemical performance as active electrodes in Li-ion batteries. These results present microwave routes as highly attractive for reproducible, gram-scale syntheses of high quality nanostructured electrodes which display close to theoretical capacity for the full iron phase

Eco-Efficient Synthesis of LiFePO4 with Different Morphologies for Li-Ion Batteries

LiFePO4 is presently the most studied electrode material for battery applications. It can be prepared via solution, although it requires well-controlled pH conditions to master the iron valence state in the newly created material. Here we report its synthesis via the use of "latent bases" capable of releasing a nitrogen base upon heating. This way of controlling the reaction pH enables, in the absence of excess Li, the preparation of Fe+3-free LiFePO4 powders having various morphologies and showing good electrochemical performance. This approach is shown to offer great opportunities for the low-temperature synthesis of various electrode materials

Novel polyoxometalates: Is antimony the new molybdenum?

Polyoxometalates based on Mo, W or V have been known for a long time and present a diverse range of structures, with the [XMo₁₂O₄₀]ⁿ⁻ Keggin ions (X = P, Si ,…) perhaps the best known.¹ They are still subject to intense research with >4000 papers published in the past five years. Following on from our study² of aryl arsonic acids RAsO₃H₂, which are straightforward molecular species based on four-coordinate As(V), we became interested in the corresponding antimony compounds. Although aryl stibonic acids of nominal formula RSbO₃H₂ have been known for over 100 years,³ their composition has remained uncertain, as they form only amorphous solids, have complicated titration behaviour and only limited solubility. The presumption has been that they are polymeric, based on 5- or 6-coordinate Sb with Sb-O-Sb linkages, though direct evidence is sparse.⁴ Recently, it has been shown by Beckman that if very bulky R groups are used, then relatively simple dimers such as (2,6-Mes₂C₆H₃Sb₂O₂(OH)₄(Mes=mesityl) can be isolated, but these represent a special case.

In-situ solvothermal processing of polycaprolactone/hydroxyapatite nanocomposites with enhanced mechanical and biological performance for bone tissue engineering

The interest in biodegradable polymer-matrix nanocomposites with bone regeneration potential has been increasing in recent years. In the present work, a solvothermal process is introduced to prepare hydroxyapatite (HA) nanorod-reinforced polycaprolactone in-situ. A non-aqueous polymer solution containing calcium and phosphorous precursors is prepared and processed in a closed autoclave at different temperatures in the range of 60–150 °C. Hydroxyapatite nanorods with varying aspect ratios are formed depending on the processing temperature. X-ray diffraction analysis and field-emission scanning electron microscopy indicate that the HA nanorods are semi-crystalline. Energy-dispersive X-ray spectroscopy and Fourier transform infrared spectrometry determine that the ratio of calcium to phosphorous increases as the processing temperature increases. To evaluate the effect of in-situ processing on the mechanical properties of the nanocomposites, highly porous scaffolds (>90%) containing HA nanorods are prepared by employing freeze drying and salt leaching techniques. It is shown that the elastic modulus and strength of the nanocomposites prepared by the in-situ method is superior (∼15%) to those of the ex-situ samples (blended HA nanorods with the polymer solution). The enhanced bone regeneration potential of the nanocomposites is shown via an in vitro bioactivity assay in a saturated simulated body fluid. An improved cell viability and proliferation is also shown by employing (3-(4,5- dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide) (MTT) assay in human osteosarcoma cell lines. The prepared scaffolds with in vitro regeneration capacity could be potentially useful for orthopaedic applications and maxillofacial surgery

Chemical solution deposition of functional ceramic coatings using ink-jet printing

This paper discusses the development of environmentally-friendly precursor inks suited for ink-jet printing of functional ceramic coatings. We synthesized superconducting materials, SrTiO3 thin films for coated conductor applications and transparent TiO2 photocatalytic coatings. Here, we discuss all aspects of ink formulation, including the stabilization of metal ions, nanoparticle inks or combination of both. This demands the investigation and determination of the inks rheological parameters. Ceramic nanoparticles are often incorporated in our inks to decrease thermal processing temperatures (e.g., TiO2 or YSZ coatings...) or enhance the properties of the functional ceramic coating (e.g., pinning centres in superconducting coatings). These ceramic nanoparticles (ZrO2, HfO2, TiO2...) are synthesized through methods based on microwave heating from aqueous and/or organic solutions. With that, we aim at developing smart and environmentally friendly processes that require lower energy input