Multiple-Yolk-Shell NiO Microspheres for Selective Detection of m-Xylene.

m-Xylene is a volatile organic compound that is extensively used in various industrial processes. It is toxic, posing significant risks to human health and the environment. Therefore, developing gas sensors with high sensitivity and selectivity for m-xylene detection is critical. In this work, we demonstrated the synthesis of NiO-yolk double-shell (NiO-YDS) and NiO-yolk triple-shell (NiO-YTS) derived from NiO/Ni-BTC and NiO/Ni-PTA composites, respectively, using the microwave-assisted solvothermal method from Ni-BTC-derived NiO spheres. The NiO/Ni-BTC composite has trimesic acid (H3BTC) as an organic linker, while NiO/Ni-PTA has p-terephthalic acid (PTA). We investigated the sensing properties of these materials for 2-butanone, 2-nonanone, 3-methyl-1-butanol, acetone, benzene, ethanol, methanol, and m-xylene. These composites exhibited excellent sensitivity and selectivity for detecting m-xylene under dry conditions. Specifically, the NiO-YTS sensor showed a sensitivity of 217.5% to m-xylene, while the NiO-YDS sensor demonstrated a sensitivity of 179.8% at 350 °C in dry air. We emphasize the NiO-YTS composite due to its superior sensitivity and selectivity in detecting m-xylene compared with the NiO-YDS composite. The NiO-YTS sensor exhibited stable and reproducible sensing performance for 100 ppm of m-xylene under optimum working conditions, with a theoretical detection limit of 5.43 ppb and relatively fast response time (89 s) and recovery time (191 s). This work describes an easy method for synthesizing NiO-YDS and NiO-YTS derived from NiO/Ni-BTC and NiO/Ni-PTA composites. It demonstrates that these composites represent a new class of materials that can potentially enhance the sensitivity and selectivity of m-xylene gas sensors.

Nanoparticulated WO3/NiWO4 Using Cellulose as a Template and Its Application as an Auxiliary Co-Catalyst to Pt for Ethanol and Glycerol Electro-Oxidation.

This work reports the use of cellulose as a template to prepare nanosized WO3 or NiWO4 and its application as a co-catalyst in the electro-oxidation of ethanol and glycerol. Microcrystalline cellulose was hydrolyzed with phosphotungstic acid (H3PW12O40) to prepare the nanocrystalline cellulose template. The latter was air-calcinated to remove the template and obtain nanometric WO3. Tungsten oxide was impregnated with Ni(NO3)2, which was subsequently air-calcinated to obtain the nanometric NiWO4. Elemental analysis confirmed the coexistence of nickel and tungsten, whereas thermal analysis evidenced a high thermal stability for these materials. The X-ray diffractograms displayed crystal facets of WO3 and, when Ni(II) was added, NiWO4. The transmission electron micrographs corroborated the formation of nanosized particles with average particle sizes in the range of 30 to 50 nm. Finally, to apply this material, Pt/WO3-C and Pt/WO3-NiWO4-C were prepared and used in ethanol and glycerol electro-oxidation in an alkaline medium, observing a promotional effect of the oxide and tungstate by reducing the onset potential and increasing the current density. These materials show great potential to produce clean electricity or green hydrogen, contributing to energetic transition.

Magnetic properties of Fe-doped NiO nanoparticles.

Undoped and Fe-doped NiO nanoparticles were successfully synthesized using a lyophilization method and systematically characterized through magnetization techniques over a wide temperature range, with varying intensity and frequency of the applied magnetic fields. The Ni1-xFexO nanoparticles can be described by a core-shell model, which reveals that Fe doping enhances exchange interactions in correlation with nanoparticle size reduction. The nanoparticles exhibit a superparamagnetic blocking transition, primarily attributed to their cores, at temperatures ranging from above room temperature to low temperatures, depending on the Fe-doping level and sample synthesis temperature. The nanoparticle shells also exhibit a transition at low temperatures, in this case to a cluster-glass-like state, caused by the dipolar magnetic interactions between the net magnetic moments of the clusters. Their freezing temperature shifts to higher temperatures as the Fe-doping level increases. The existence of an exchange bias interaction was observed, thus validating the core-shell model proposed.

Study of the Electronic Interaction between NiO and Short Polythiophene Chains towards Solar Photon Harvesting.

The sustainable production of energy is a field of interest to which a new requirement is now imposed: the need to be respectful of the environment. New materials and techniques are being developed, but environmental concerns impose the necessity of keeping research active towards the development of green energy. For this reason, we present the study of short polythiophene (PTh) chains (three and five monomers) and their interaction with nickel oxide, looking for properties related to solar photon harvesting in order to produce electricity. The models of the molecules were developed, and the calculations were performed with an M11-L meta-GGA functional, specially developed for electronic structure calculations. The theoretical explorations demonstrated that the geometry of the PTh molecules suffer little distortion when interacting with the NiO molecule. The calculated value of Eg lies between 2.500 and 0.412 eV for a three-ring PTh chain and between 1.944 and 0.556 eV for a five-ring PTh chain. The chemical parameters indicated that, depending on the geometry of the system, the chemical potential varies from 81.27 to 102.38 kcal/mol and the highest amount of electronic charge varies from -2.94 to 21.56 a.u. for three-monomer systems. For five-monomer systems, the values lie within similar ranges as those of the three-monomer systems. The Partial Density of States (PDOS) showed that the valence and conduction electronic bands were composed of states in the NiO and PTh rings, except for a system where there was a non-bonding interaction.

Fabrication of Li-Doped NiO Thin Films by Ultrasonic Spray Pyrolysis and Its Application in Light-Emitting Diodes.

The fabrication of NiO films by different routes is important to extend and improve their applications as hole-transporting layers in organic and inorganic optoelectronic devices. Here, an automated ultrasonic pyrolysis spray method was used to fabricate NiO and Li-doped NiO thin films using nickel acetylacetonate and lithium acetate dihydrate as metal precursor and dimethylformamide as solvent. The effect of the amount of lithium in the precursor solution on the structural, morphological, optical, and electrical properties were studied. XRD results reveal that all the samples are polycrystalline with cubic structure and crystallite sizes in the range of 21 to 25 nm, without any clear trend with the Li doping level. AFM analysis shows that the crystallites form round-shaped aggregates and all the films have low roughness. The optical transmittance of the films reaches values of 60% to 77% with tendency upward as Li content is increased. The electrical study shows that the films are p-type, with the carrier concentration, resistivity, and carrier mobility depending on the lithium doping. NiO:Li (10%) films were successfully incorporated into inorganic light emitting diodes together with Mn-doped ZnS and ZnO:Al films, all deposited on ITO by the same ultrasonic spray pyrolysis technique.

Incorporation of NiO into SiO2, TiO2, Al2O3, and Na4.2Ca2.8(Si6O18) Matrices: Medium Effect on the Optical Properties and Catalytic Degradation of Methylene Blue.

The medium effect of the optical and catalytic degradation of methylene blue was studied in the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites, which were prepared by a solid-state method. The new composites were characterized by XRD (X-ray diffraction of powder), SEM/EDS, TEM, and HR-TEM. The size of the NiO nanoparticles obtained from the PSP-4-PVP (polyvinylpyrrolidone) precursors inside the different matrices follow the order of SiO2 > TiO2 > Al2O3. However, NiO nanoparticles obtained from the chitosan precursor does not present an effect on the particle size. It was found that the medium effect of the matrices (SiO2, TiO2, Al2O3, and Na4.2Ca2.8(Si6O18)) on the photocatalytic methylene blue degradation, can be described as a specific interaction of the NiO material acting as a semiconductor with the MxOy materials through a possible p-n junction. The highest catalytic activity was found for the TiO2 and glass composites where a favorable p-n junction was formed. The isolating character of Al2O3 and SiO2 and their non-semiconductor behavior preclude this interaction to form a p-n junction, and thus a lower catalytic activity. NiO/SiO2 and NiO/Na4.2Ca2.8(Si6O18) showed a similar photocatalytic behavior. On the other hand, the effect of the matrix on the optical properties for the NiO/SiO2, NiO/TiO2, NiO/Al2O3, and NiO/Na4.2Ca2.8(Si6O18) composites can be described by the different dielectric constants of the SiO2, TiO2, Al2O3, Na4.2Ca2.8(Si6O18) matrices. The maxima absorption of the composites (λmax) exhibit a direct relationship with the dielectric constants, while their semiconductor bandgap (Eg) present an inverse relationship with the dielectric constants. A direct relationship between λmax and Eg was found from these correlations. The effect of the polymer precursor on the particle size can explain some deviations from this relationship, as the correlation between the particle size and absorption is well known. Finally, the NiO/Na4.2Ca2.8(Si6O18) composite was reported in this work for the first time.

Simultaneous determination of paracetamol and ciprofloxacin in biological fluid samples using a glassy carbon electrode modified with graphene oxide and nickel oxide nanoparticles.

A simple and highly selective electrochemical method using a glassy carbon electrode (GCE) modified with graphene oxide (GO) and nickel oxide nanoparticles (NiONPs) was developed for the simultaneous determination of paracetamol (PAR) and ciprofloxacin (CIP). The electrochemical characterisation of the modified GCE was performed by cyclic voltammetry and electrochemical impedance spectroscopy. The morphological characterisation of the GO and NiONPs was performed by scanning electron microscopy and transmission electron microscopy. Under optimised conditions, using square wave voltammetry, the simultaneous determination of PAR and CIP using the NiONPs-GO-CTS: EPH/GCE sensor shows a linear concentration range from 0.10 to 2.9µmolL-1 and 0.040-0.97µmolL-1, with detection limits of 6.7 and 6.0 nmol L-1, respectively. The NiONPs-GO-CTS: EPH/GCE sensor showed good reproducibility, repeatability and stability. Furthermore, the proposed method was successfully applied for the simultaneous determination of PAR and CIP in synthetic biological fluid samples.

Self-Functionalization Behind a Solution-Processed NiOx Film Used As Hole Transporting Layer for Efficient Perovskite Solar Cells.

Fabrication of solution-processed perovskite solar cells (PSCs) requires the deposition of high quality films from precursor inks. Frequently, buffer layers of PSCs are formed from dispersions of metal oxide nanoparticles (NPs). Therefore, the development of trustable methods for the preparation of stable colloidal NPs dispersions is crucial. In this work, a novel approach to form very compact semiconducting buffer layers with suitable optoelectronic properties is presented through a self-functionalization process of the nanocrystalline particles by their own amorphous phase and without adding any other inorganic or organic functionalization component or surfactant. Such interconnecting amorphous phase composed by residual nitrate, hydroxide, and sodium ions, proved to be fundamental to reach stable colloidal dispersions and contribute to assemble the separate crystalline nickel oxide NPs in the final film, resulting in a very homogeneous and compact layer. A proposed mechanism behind the great stabilization of the nanoparticles is exposed. At the end, the self-functionalized nickel oxide layer exhibited high optoelectronic properties enabling perovskite p-i-n solar cells as efficient as 16.6% demonstrating the pertinence of the presented strategy to obtain high quality buffer layers processed in solution at room temperature.