Antonio Ribera

Hexagonal nanosheets from the exfoliation of Ni2+-Fe3+ LDHs: a route towards layered multifunctional materials

Here we report the synthesis of a crystalline micrometric-sized hexagonal-shaped Ni2+-Fe3+ LDH by following a modified homogeneous precipitation method. The exfoliation of the material in formamide leads to stable suspensions of hexagonal nanometric sheets, which have been extensively characterized. Our data confirm that the intrinsic properties of the bulk material are retained by these segregated nanosheets, thus opening the door for their use in the development of layered multifunctional materials.

Spontaneous Magnetization in Ni-Al and Ni-Fe Layered Double Hydroxides

Layered double hydroxides containing paramagnetic Ni (II) and diamagnetic/paramagnetic Al (III)/Fe (III) ions have been prepared and characterized. Ni 2Al(OH) 6(NO 3). nH 2O ( 1), Ni 2Fe(OH) 6(NO 3). nH 2O ( 2), Ni 2Fe(OH) 6(C 6H 8O 4) 0.5. nH 2O ( 3), and Ni 2Fe(OH) 6(C 10H 16O 4) 0.5. nH 2O ( 4) were prepared by coprecipitation at controlled pH as polycrystalline materials with the typical brucite-like structure, with alternating layers of hydroxide and the corresponding anions, which determine the interlayer separation. Magnetic studies show the appearance of spontaneous magnetization between 2 and 15 K for these compounds. Interestingly, the onset temperature for spontaneous magnetization follows a direct relationship with interlayer separation, since this is the only magnetic difference between compounds 2, 3, and 4. Magnetic and calorimetric data indicate that long-range magnetic ordering is not occurring in any of these materials, but rather a freezing of the magnetic system in 3D due to the magnetic disorder and competing intra- and interlayer interactions. Thus, these hydrotalcite-like magnetic materials can be regarded as spin glasses.

Synthesis, characterization and magnetism of monodispersed water soluble palladium nanoparticles

Water soluble, monodispersed Pd nanoparticles with a narrow particle size distribution have been successfully synthesized by controlled reduction of [PdCl4]2−. The resulting aqueous colloids are stable over extended periods of time and can be prepared at high nanoparticle loading (20 g/L of Pd) with no agglomeration. The size of the nanoparticles can be reduced from the nanometer (ca. 3.5 nm) to the sub-nanometer size range (ca. 0.9 nm). Detailed magnetic characterization indicated that the larger, 3.5 nm nanoparticles show ferromagnetic properties at room temperature, while the sub-nanometric ones lose this magnetic behavior.

Preconcentration of emerging contaminants in environmental water samples by using silica supported Fe3O4 magnetic nanoparticles for improving mass detection in capillary liquid chromatography

A magnetic material based on Fe(3)O(4) magnetic nanoparticles incorporated in a silica matrix by using a sol-gel procedure has been used to extract and preconcentrate emerging contaminants such as acetylsalicylic acid, acetaminophen, diclofenac and ibuprofen from environmental water samples prior to the analysis with Capillary LC-MS. The use of the proposed silica supported Fe(3)O(4) magnetic nanoparticles enables surfactant free extracts for the analysis with MS detection without interferences in the ionisation step. Under the optimum conditions, we demonstrated the reusability of the magnetic sorbent material during 20 uses without loss in the extraction efficiency. In addition, no cleanup was necessary. The preconcentration factor was 100 and the detection limits were between 50 and 150 ng/L. The proposed procedure has been applied to the analysis of water samples obtaining recoveries between 80 and 110% and RSD values lower than 12%. Concentrations of the target analytes over the range 1.7 and 0.1 μg/L have been found in different water samples.

Magnetic In-Tube Solid Phase Microextraction

We report a new in-tube solid phase microextraction approach named magnetic in-tube solid phase microextraction, magnetic-IT-SPME. Magnetic-IT-SPME has been developed, taking advantage of magnetic microfluidic principles with the aim to improve extraction efficiency of IT-SPME systems. First, a magnetic hybrid material formed by Fe(3)O(4) nanoparticles supported on SiO(2) was synthesized and immobilized in the surface of a bared fused silica capillary column to obtain a magnetic adsorbent extraction phase. The capillary column was placed inside a magnetic coil that allowed the application of a variable magnetic field. Acetylsalicylic acid, acetaminophen, atenolol, diclofenac, and ibuprofen were tested as target analytes. The application of a controlled magnetic field resulted in quantitative extraction efficiencies of the target analytes between 70 and 100%. These results demonstrated that magnetic forces solve the low extraction efficiency (10-30%) of IT-SPME systems, which is one of their main drawbacks.

Interplay between Chemical Composition and Cation Ordering in the Magnetism of Ni/Fe Layered Double Hydroxides

We report the synthesis of a family of ferrimagnetic NiFe layered double hydroxides (LDHs) with a variable Ni(2+)/Fe(3+) in-plane composition of [Ni(1-x)Fe(x)(OH)2](CO3)(x/2)·yH2O (x = 0.20, 0.25, and 0.33) by following a modified homogeneous precipitation. These layered magnets display high crystallinity, homogeneous hexagonal morphologies, and micrometric size that enable their quantitative exfoliation into single layers by sonomechanical treatment of the solids in polar solvents. This was confirmed by dynamic light scattering, UV-vis spectroscopy, high-resolution transmission electron miscroscopy, and atomic force microscopy methodologies to study the resulting steady suspensions. Our magnetic study reflects that the iron content in the LDH layers controls the overall magnetism of these lamellae. Hence, the gradual replacement of Ni(2+) with Fe(3+) centers introduces a larger amount of antiferromagnetically coupled Fe-OH-Fe pairs across the layers, provoking that the compound with the highest Fe/Ni ratio displays spontaneous magnetization at higher temperatures (T(irr) = 15.1 K) and the hardest coercive field (3.6 kG). Mössbauer spectroscopy confirms that the cation distribution in the layers is not random and reflects the occurrence of Fe clustering due to the higher affinity of Fe(3+) ions to accommodate other homometallic centers in their surroundings. In our opinion, this clarifies the origin of the glassy behavior, also reported for other magnetic LDHs, and points out spin frustration as the most likely cause.

Silica supported Fe(3)O(4) magnetic nanoparticles for magnetic solid-phase extraction and magnetic in-tube solid-phase microextraction: application to organophosphorous compounds.

This work demonstrates the application of silica supported Fe3O4 nanoparticles as sorbent phase for magnetic solid-phase extraction (MSPE) and magnetic on-line in-tube solid-phase microextraction (Magnetic-IT-SPME) combined with capillary liquid chromatography–diode array detection (CapLC-DAD) to determine organophosphorous compounds (OPs) at trace level. In MSPE, magnetism is used as separation tool while in Magnetic-IT-SPME, the application of an external magnetic field gave rise to a significant improvement of the adsorption of OPs on the sorbent phase. Extraction efficiency, analysis time, reproducibility and sensitivity have been compared. This work showed that Magnetic-IT-SPME can be extended to OPs with successful results in terms of simplicity, speed, extraction efficiency and limit of detection. Finally, wastewater samples were analysed to determine OPs at nanograms per litre.

Layered double hydroxide (LDH)–organic hybrids as precursors for low-temperature chemical synthesis of carbon nanoforms

A low-temperature route for the chemical synthesis of diverse carbon nanoforms, including nano-onions and multi-walled nanotubes, is described. The method involves thermal decomposition of a sebacate-intercalated NiFe LDH at 400 °C and benefits from the catalytic activity of FeNi3 nanoparticles generated in situ.

Electrochemical characterization of iron sites in ex-framework FeZSM-5

Abstract The electrochemical response of FeZSM-5 prepared by an ex -framework method has been studied using Paraloid B72 polymer film electrodes immersed in aqueous media using H 2 SO 4 , HCl, Na 2 EDTA and NaCl electrolytes. The ex -framework method comprises the hydrothermal synthesis of isomorphously substituted FeZSM-5, followed by calcination at 823 K and subsequent steam treatment (300 mbar H 2 O in N 2 ) at 873 K. During this process iron is extracted to extra-framework positions. Also partial dealumination of the zeolite framework takes place. Characteristic voltammetric responses in the +1.0 to −0.6 V versus SCE potential range have been recorded and were used to characterize the iron species present in the materials during the different preparation stages. Different species were identified, including tetrahedral framework iron, octahedral extra-framework iron ions, dimeric or oligomeric iron oxo-complexes, and iron oxide nano-aggregates. Iron oxide nano-aggregates displayed reductive or oxidative dissolution processes, while framework iron species displayed one electron transfer processes involving Fe(III) and Fe(II) species confined to boundary sites of the zeolite matrix.

Confined growth of cyanide-based magnets in two dimensions.

Herein we report the first hybrid magnetic material resulting from the intercalation of a cyanide-based molecular magnet into a solid-state layered host. More specifically, the use of a diamagnetic cationic Zn(II)-Al(lII) layered double hydroxide host allows for the formation of an anionic two-dimensional ferromagnetic Ni(II)-Cr(III) Prussian Blue analogue, from the templated assembly of its ionic molecular components in the confined interlamellar space offered by the inorganic host.