J. P. Araújo

Effect of diamagnetic Ca, Sr, Pb, and Ba substitution on the crystal structure and multiferroic properties of the BiFeO3 perovskite

In this work, we studied the effect of heterovalent Ca, Sr, Pb, and Ba substitution on the crystal structure, dielectric, local ferroelectric, and magnetic properties of the BiFeO3 multiferroic perovskite. Ceramic solid solutions with the general formula Bi0.7A0.3FeO3 (A is a doping element) were prepared and characterized by x-ray diffraction, dielectric, piezoresponse force microscopy (PFM), and magnetic measurements. It is shown that the crystal structure of the compounds is described within the space group R3c, permitting the spontaneous polarization, whose existence was confirmed by the PFM data. Magnetic properties of the solid solutions are determined by the ionic radius of the substituting element. Experimental results suggest that the increase in the radius of the A-site ion leads to the effective suppression of the spiral spin structure of BiFeO3, resulting in the appearance of net magnetization.

Nanoporous alumina as templates for multifunctional applications

Due to its manufacturing and size tailoring ease, porous anodic alumina (PAA) templates are an elegant physical-chemical nanopatterning approach and an emergent alternative to more sophisticated and expensive methods currently used in nanofabrication. In this review, we will describe the ground work on the fabrication methods of PAA membranes and PAA-based nanostructures. We will present the specificities of the electrochemical growth processes of multifunctional nanomaterials with diversified shapes (e.g., nanowires and nanotubes), and the fabrication techniques used to grow ordered nanohole arrays. We will then focus on the fabrication, properties and applications of magnetic nanostructures grown on PAA and illustrate their dependence on internal (diameter, interpore distance, length, composition) and external (temperature and applied magnetic field intensity and direction) parameters. Finally, the most outstanding experimental findings on PAA-grown nanostructures and their trends for technological appl...

Designing Novel Hybrid Materials by One-Pot Co-condensation: From Hydrophobic Mesoporous Silica Nanoparticles to Superamphiphobic Cotton Textiles

This work reports the synthesis and characterization of mesoporous silica nanoparticles (MSNs) functionalized with tridecafluorooctyltriethoxysilane (F13) and their in situ incorporation onto cotton textiles. The hybrid MSNs and the functional textiles were prepared by a one-pot co-condensation methodology between tetraethylorthosilicate (TEOS) and F13, with hexadecyltrimethylammonium chloride (CTAC) as the template and triethanolamine as the base. The influence of the F13 to TEOS molar ratio (1:10, 1:5 and 1:3) on the nanoparticle morphology, porosity, degree of functionalization, and hydro/oleophobic properties is discussed. The hybrid nanosilicas presented high colloidal stability and were spherical and monodispersed with average particle size of ∼45 nm. They also showed high surface areas, large pore volumes, and a wormhole-type mesoporous structure. The increase in the organosilane proportion during the co-condensation process led to a more radially branched wormhole-like mesoporosity, a decrease in the surface area, pore volume, and amount of surface silanol groups, and an enrichment of the surface with fluorocarbon moieties. These changes imparted hydrophobic and oleophobic properties to the materials, especially to that containing the highest F13 loading. Cotton textiles were coated with the F13-MSNs through an efficient and less time-consuming route. The combination between surface roughness and mesoporosity imparted by the MSNs, and the low surface energy provided by the organosilane resulted in superhydrophobic functional textiles. Moreover, the textile with the highest loading of fluorocarbon groups was superamphiphobic.

Size and surface effects on the magnetic properties of NiO nanoparticles

NiO nanoparticles (NPs) were prepared by a sol-gel process using the citrate route. The sol-gel parameters were tuned to obtain samples with different average particle sizes, ranging from 12 to 70 nm. Magnetic characterization revealed an increase in the blocking temperature with the diameter of the NPs and an increase in the effective magnetic anisotropy (K(eff)) with decreasing particle size. The magnetic moment per particle was calculated for all samples using the susceptibility value at T = 300 K. The number of uncompensated spins per NP was found to be proportional to n (n(S)≡ total number of spins), indicating that they are randomly distributed on the NP surface. For small diameters (<30 nm) the surface anisotropy constant was estimated, using, for NiO NPs, a recent model describing the evolution of K(eff) with particle size. Hysteretic loops performed at low temperatures after field cooling displayed loop shifts (∼6.5 kOe in the field axis and ∼0.18 emu g(-1) vertically), coercive field enhancement (H(C)≈ 4.8 kOe) and training effects for the smaller NPs. The sample with NPs of larger diameters presented magnetic properties close to those of bulk NiO.

Intrinsic nature of the magnetization enhancement in heterovalently doped Bi1−xAxFeO3 (A = Ca, Sr, Pb, Ba) multiferroics

The mechanism of the formation of heterovalent-substitution-induced defects as well as their influence on the magnetic properties of BiFeO3-based multiferroics has been studied. It has been shown that heterovalent A2+ substitution results in the formation of oxygen vacancies in the host lattices of both antiferromagnetic and weak ferromagnetic Bi1−xAxFeO3 (A = Ca, Sr, Pb, Ba; x = 0.2, 0.3) compounds, thus indicating the intrinsic (i.e. not related to defects themselves) mechanism of doping-induced enhancement of magnetization. A correlation between the ionic radius of the substituting element and the value of the spontaneous magnetization of the corresponding solid solution has been found. The experimental results suggest that A-site substitution with the biggest ionic radius ions effectively suppresses the spiral spin configuration of antiferromagnetic BiFeO3.

Rhombohedral-to-orthorhombic transition and multiferroic properties of Dy-substituted BiFeO3

Investigation of crystal structure, ferroelectric, and magnetic properties of polycrystalline Bi1−xDyxFeO3 (0.1≤x≤0.2) samples was carried out. X-ray diffraction study revealed composition-driven rhombohedral-to-orthorhombic R3c→Pnma phase transition at x∼0.15. Both structural phases were found to coexist in a broad concentration range. Piezoresponse force microscopy found suppression of the parent ferroelectric phase upon dysprosium substitution. Magnetometric study confirmed that the A-site doping induces appearance of a weak ferromagnetic behavior. Both the ferroelectric and magnetic properties were shown to correlate with a structural evolution.

Magnetic interactions and reversal mechanisms in Co nanowire and nanotube arrays

Ordered hexagonal arrays of Co nanowires (NWs) and nanotubes (NTs), with diameters between 40 and 65 nm, were prepared by potentiostatic electrodeposition into suitably modified nanoporous alumina templates. The geometrical parameters of the NW/NT arrays were tuned by the pore etching process and deposition conditions. The magnetic interactions between NWs/NTs with different diameters were studied using first-order reversal curves (FORCs). From a quantitative analysis of the FORC measurements, we are able to obtain the profiles of the magnetic interactions and the coercive field distributions. In both NW and NT arrays, the magnetic interactions were found to increase with the diameter of the NWs/NTs, exhibiting higher values for NW arrays. A comparative study of the magnetization reversal processes was also performed by analyzing the angular dependence of the coercivity and correlating the experimental data with theoretical calculations based on a simple analytical model. The magnetization in the NW array...

On the stability enhancement of cuprous oxide water splitting photocathodes by low temperature steam annealing

Given the intermittent nature of solar radiation, the large-scale use of solar energy requires an efficient energy storage solution. So far, the only practical way to store such large amounts of energy is in the form of a chemical energy carrier, i.e., a fuel. Photoelectrochemical (PEC) cells offer the ability to convert solar energy directly into chemical energy in the form of hydrogen. Cuprous oxide (Cu2O) is being investigated for photoelectrochemical solar water splitting since it has a band gap of 2.0 eV with favorable energy band positions for water cleavage; it is abundant and environmentally friendly. A major challenge with Cu2O is its limited chemical stability in aqueous environments. We present a simple and low-cost treatment to create a highly stable photocathode configuration for H2 production, consisting of steam treatment of the multilayer structures. The role of this treatment was investigated and the optimized electrodes have shown photocurrents over −5 mA cm−2 with 90% stability over more than 50 h of light chopping (biased at 0 VRHE in pH 5 electrolyte).

Star-shaped magnetite@gold nanoparticles for protein magnetic separation and SERS detection

A novel synthetic methodology for star shaped gold-coated magnetic nanoparticles is reported. The coating is performed in two steps: formation of gold nuclei at the surface of magnetite nanoparticles followed by growth of the gold nuclei into a complete star shaped shell. The star-shaped gold-coated magnetic nanoparticles thus obtained preserve the magnetic properties of the precursor magnetite nanoparticles, e.g. they can be easily separated with a magnet. In addition, the gold coating provides interesting optical properties while simultaneously allowing for biofunctionalization that may be advantageous for biological applications, such as (bio)detection via surface-enhanced Raman spectroscopy (SERS). As a proof-of-concept, a capping agent terminated with a nickel(II)-nitrilotriacetate group showing high affinity for histidine was used to modify the surface of the nanoparticles. The resulting star-shaped nanoparticles were used to selectively capture histidine-tagged maltose-binding protein from a crude cell extract. Finally, the performance of star shaped gold-coated magnetic nanoparticles as SERS platforms was demonstrated through the detection of Raman active dye (Astra Blue).

Tunning pore filling of anodic alumina templates by accurate control of the bottom barrier layer thickness

The role of the alumina barrier layer thickness (δ(b)) on the growth of Ni nanowires (NWs) in porous anodic alumina (PAA) has been revealed. By varying the final anodization voltage to form dendrites at the bottom of the nanoporous structure, we are able to optimize δ(b) (in the 2-16 nm range), allowing us to obtain a Ni pore filling percentage (f(p)) of almost 100% for δ(b) = 10 nm. However, deviations from this optimal δ(b)-value led to a strong decrease of f(p). Moreover, an increase of the electrodeposition efficiency (EE) and NW homogeneity was also verified for δ(b) up to 10 nm. Such increase in nominal δ(b) leads to a consistent growth rate in all pores and consequently a complete and uniform nanopore filling. On the other hand, the decrease in electrodeposition efficiency visible for δ(b) > 10 nm is related with hydrogen evolution and dielectric breakdown of the insulator layer due to the required high deposition voltages. Non-uniform NW growth is then visible, with the consequent decrease in f(p). The control of the pore filling and length homogeneity of the fabricated 1D metallic nanostructures, combined with the ability to adjust the pore dimensions of PAA, can bring novel approaches for the fabrication of nano-objects and thus exciting new applications.