Open Access
Steering the synthesis of Fe3O4 nanoparticles under sonication by using a fractional factorial design
(Elsevier, 2021) Echeverría Morrás, Jesús; Moriones Jiménez, Paula; Garrido Segovia, Julián José; Ugarte Martínez, María Dolores; Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Gómez Polo, Cristina; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Estadística, Informática y Matemáticas; Estatistika, Informatika eta Matematika; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa; Gobierno de Navarra / Nafarroako Gobernua
Superparamagnetic iron oxide nanoparticles (MNPs) have the potential to act as heat sources in magnetic hyperthermia. The key parameter for this application is the specific absorption rate (SAR), which must be as large as possible in order to optimize the hyperthermia treatment. We applied a Plackett-Burman fractional factorial design to investigate the effect of total iron concentration, ammonia concentration, reaction temperature, sonication time and percentage of ethanol in the aqueous media on the properties of iron oxide MNPs. Characterization techniques included total iron content, Fourier Transform Infrared Spectroscopy, X-Ray Diffraction, High Resolution Transmission Electron Microscopy, and Dynamic Magnetization. The reaction pathway in the coprecipitation reaction depended on the initial Fe concentration. Samples synthesized from 0.220 mol L−1 Fe yielded magnetite and metastable precipitates of iron oxyhydroxides. An initial solution made up of 0.110 mol L−1 total Fe and either 0.90 or 1.20 mol L−1 NH3(aq) led to the formation of magnetite nanoparticles. Sonication of the reaction media promoted a phase transformation of metastable oxyhydroxides to crystalline magnetite, the development of crystallinity, and the increase of specific absorption rate under dynamic magnetization.
Open Access
Magnetic-field-assisted photocatalysis of N-TiO2 nanoparticles
(IEEE, 2023-09-04) Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Beato López, Juan Jesús; Pérez de Landazábal Berganzo, José Ignacio; Gómez Polo, Cristina; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
Nitrogen doped TiO2 nanoparticles were synthesized through solvothermal method employing Ti (IV) butoxide and HNO3 as precursors. Structural and optical characterizations confirm their nanometer nature (sizes around 10 nm) and the band-gap energy values in the UV range (3.2 eV). Nitrogen doping enhances the occurrence of optical Urbach tails extending towards the visible region. Visible photocatalytic performance (degradation of methyl orange) is correlated with maximum values in the magnetic susceptibility linked to a magnetic polarization of the anatase structure via defects (oxygen vacancies). The application of magnetic field provides a positive effect (acceleration in reaction kinetics) within the UV-Vis range.
Open Access
Magnetic carbon Fe3O4 nanocomposites synthesized via magnetic induction heating
(Springer Nature, 2023) Cervera Gabalda, Laura María; Gómez Polo, Cristina; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra/Nafarroako Unibertsitate Publikoa
Magnetic Induction Heating (MIH) of magnetite nanoparticles is employed as a novel synthesis procedure of carbon based magnetic nanocomposites. Magnetic nanoparticles (Fe3O4) and fructose (1:2 weight ratio) were mechanically mixed and submitted to a RF magnetic field (305 kHz). The heat generated by the nanoparticles leads to the decomposition of the sugar and to the formation of an amorphous carbon matrix. Two sets of nanoparticles, with mean diameter sizes of 20 and 100 nm, are comparatively analysed. Structural (X-ray diffraction, Raman spectroscopy, Transmission Electron Microscopy (TEM)), electrical and magnetic (resistivity, SQUID magnetometry) characterizations confirm the nanoparticle carbon coating through the MIH procedure. The percentage of the carbonaceous fraction is suitably increased controlling the magnetic heating capacity of the magnetic nanoparticles. The procedure enables the synthesis of multifunctional nanocomposites with optimized properties to be applied in different technological fields. Particularly, Cr (VI) removal from aqueous media is presented employing the carbon nanocomposite with 20 nm Fe3O4 nanoparticles.
Open Access
Fe3O4-SiO2 mesoporous core/shell nanoparticles for magnetic field-induced ibuprofen-controlled release
(American Chemical Society, 2022-12-23) García Rodríguez, Lucía; Garayo Urabayen, Eneko; López Ortega, Alberto; Galarreta Rodríguez, Itziar; Cervera Gabalda, Laura María; Cruz Quesada, Guillermo; Cornejo Ibergallartu, Alfonso; Garrido Segovia, Julián José; Gómez Polo, Cristina; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa, PJUPNA2020; Gobierno de Navarra / Nafarroako Gobernua
Hybrid magnetic nanoparticles made up of an iron oxide, Fe3O4, core and a mesoporous SiO2 shell with high magnetization and a large surface area were proposed as an efficient drug delivery platform. The core/shell structure was synthesized by two seed-mediated growth steps combining solvothermal and sol—gel approaches and using organic molecules as a porous scaffolding template. The system presents a mean particle diameter of 30(5) nm (9 nm magnetic core diameter and 10 nm silica shell thickness) with superparamagnetic behavior, saturation magnetization of 32 emu/g, and a significant AC magnetic-field-induced heating response (SAR = 63 W/gFe3O4, measured at an amplitude of 400 Oe and a frequency of 307 kHz). Using ibuprofen as a model drug, the specific surface area (231 m2/g) of the porous structure exhibits a high molecule loading capacity (10 wt %), and controlled drug release efficiency (67%) can be achieved using the external AC magnetic field for short time periods (5 min), showing faster and higher drug desorption compared to that of similar stimulus-responsive iron oxide-based nanocarriers. In addition, it is demonstrated that the magnetic field-induced drug release shows higher efficiency compared to that of the sustained release at fixed temperatures (47 and 53% for 37 and 42 °C, respectively), considering that the maximum temperature reached during the exposure to the magnetic field is well below (31 °C). Therefore, it can be hypothesized that short periods of exposure to the oscillating field induce much greater heating within the nanoparticles than in the external solution.
Open Access
Tuning the photocatalytic performance through magnetization in Co-Zn ferrite nanoparticles
(Elsevier, 2022) Cervera Gabalda, Laura María; Zielinska-Jurek, Anna; Gómez Polo, Cristina; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa; Gobierno de Navarra / Nafarroako Gobernua
In this work, the link between the photocatalytic performance of Co-Zn ferrite nanoparticles and the net magnetic moment is analyzed. CoxZn1-xFe2O4 nanoparticles (0 ≤ x ≤ 1) were synthesized by co-precipitation method and different physicochemical techniques were employed to characterize the samples (X-ray diffraction, Transmission Electron Microscopy (TEM), BET surface area, Diffuse Reflectance Spectroscopy (DRS), Photoluminescence spectroscopy, Z-potential, SQUID magnetometry). Enhanced photocatalytic degradation (maximum degradation ratios of two emerging pollutants, phenol and toluene) are found in those nanoparticles (0.4 ≤ x ≤ 0.6) with optimum magnetic response (i.e. superparamagnetism at room temperature and high saturation magnetization). The magnetization of the nanoparticles turns out to be the determining factor in the optimization of the photocatalytic response, since there is no clear relationship with other physicochemical parameters (i.e. specific surface area, isoelectric point, band gap energy or photoluminescence). These results support the current field of research related to photocatalytic performance enhancement through magnetic field effects.
Open Access
Heatable magnetic nanocomposites with Fe3O4 nanocubes
(Elsevier, 2022-09-27) Larumbe Abuin, Silvia; Lecumberri, Cristina; Monteserín, María; Fernández, Lorea; Medrano Fernández, Ángel María; Garayo Urabayen, Eneko; Gómez Polo, Cristina; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
The development of magnetic self-heating polymers is an area of great interest for many applications. The intrinsic magnetic properties of the magnetic fillers play a key role in the final heating capability of these nanocomposites. Thus, it has been already reported the improvement of the heating efficiency on Fe3O4 magnetic nanocubes with respect to spherical nanoparticles with the similar mean size1. This result is due to the contribution of the magnetic anisotropy giving rise to higher magnetic coercivity and as consequence, higher SAR (Specific Absorption Rate) values. In this work, well- defined Fe3O4 nanocubes were synthesized through thermal decomposition processes with a mean particle diameter around 70 nm (TEM) (Fig. 1). The SAR values were estimated through the measurement of the AC hysteresis loops, obtaining values of around 900 W/g for the dispersion of the nanocubes in water and values of 350 W/g for the nanocubes dispersed in agar (0.5% wt), with a frequency of 403 kHz and a field amplitude of 30kA/m . In this case, the decrease of the SAR values is due to the inmovilization of the particles in the medium and hence, the Brownian movement of the particles. The temperature increase was also characterized, where a clear enhancement of the heating properties was obtained for nanocubes comparing with spherical nanoparticles of similar mean diameter (Fig. 2). Finally, the heating capacity of the nanocomposites (30% weight of magnetic nanoparticles) was studied through the application of an external AC magnetic field with a Helmholtz coil (319 kHz, 400A, 200G approximately, induction equipment model EasyHeat Ambrell). The effect of the thickness of the polymeric discs on the final temperature achieved was studied (2 and 4 mm thickness and 30 mm diameter). Thus, temperatures of 100 °C or 250 °C were reached after 2 min for the nanocomposites with thicknesses of 2 and 4 mm respectively.
Open Access
Electromagnetic vibrational harvester based on U-shaped ferromagnetic cantilever: a novel two-magnet configuration
(Elsevier, 2024-10-01) Gandía Aguado, David; Garayo Urabayen, Eneko; Beato López, Juan Jesús; Royo Silvestre, Isaac; Cruz Blas, Carlos Aristóteles de la; Tainta Ausejo, Santiago; Gómez Polo, Cristina; Ciencias; Zientziak; Ingeniería Eléctrica, Electrónica y de Comunicación; Ingeniaritza Elektrikoa, Elektronikoa eta Telekomunikazio Ingeniaritza; Estadística, Informática y Matemáticas; Estatistika, Informatika eta Matematika; Institute for Advanced Materials and Mathematics - INAMAT2; Institute of Smart Cities - ISC
Electromagnetic vibrational harvesters are low-cost devices featuring high-power densities and robust structures, often used for capturing the energy of environmental vibrations (civil infrastructures, transportation, human motion, etc.,). Based on Faraday’s law, energy generation relies on the modification of the magnetic field distribution within a magnetic element caused by mechanical vibrations inducing an electromotive force (EMF) in a pick-up coil. However, the practical implementation of this type of vibrational harvester is currently limited due to the reduced generated power under low-frequency vibrations. In this work, an electromagnetic vibrational harvester is experimentally characterized and analyzed employing magnetic circuit analysis. The harvester consists of a ferromagnetic U-shaped cantilever, a NdFeB magnet and a ferrite magnet used as “magnetic tip mass” to enhance the magnetic flux changes under vibrations of frequency < 100 Hz. For this configuration, an experimental voltage of ∼ 1.2 V peak-to-peak (open circuit) was obtained at a resonant frequency of 77 Hz, enabling the subsequent electronic rectification stage. Additionally, Finite Element Method (FEM) is used to explore different design possibilities including the modeling of complex geometries, mechanical properties and non-linear magnetic materials, enabling the tuning of the resonance frequency from 51 to 77 Hz, keeping constant the induced voltage.
Open Access
Antibacterial performance of Co-Zn ferrite nanoparticles under visible light irradiation
(Wiley, 2024-11-20) Gubieda, Alicia G.; Abad Díaz de Cerio, Ana; García-Prieto, Ana; Fernández-Gubieda, María Luisa; Cervera Gabalda, Laura María; Ordoqui Huesa, Eduardo; Cornejo Ibergallartu, Alfonso; Gómez Polo, Cristina; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2
BACKGROUND: To address water scarcity and promote sustainable resource management, more efficient and cost-effective water treatment solutions are necessary. Particularly, pathogens in drinking water are a topic of growing concern. One promising technology is the use of photocatalytic nanoparticles activated by visible light as antibacterial agents. This study focuses on the characterization and antibacterial properties of Co-Zn ferrite nanocatalysts, tested against Escherichia coli. RESULTS: The CoxZn1¿xFe2O4 (x = 0, 0.1, 0.4 and 0.6) ferrites were synthesized by the co-precipitation method. Structural, morphological and optical analyses confirmed that these nanoparticles have a cubic spinel structure, with sizes of around 10 nm, and band gap energies suitable for visible light activation (1.4¿1.7 eV). The antibacterial efficacy of the nanoparticles against E. coli was tested and compared with their photocatalytic performance employing phenol as organic pollutant model (highest phenol degradation for x = 0.6). Specifically, the antibacterial capacity of these nanoparticles was evaluated by comparing the ability of bacteria to grow after being incubated with the nanoparticles under visible light and in the dark. It was found that nanoparticles with lower cobalt content (x = 0 and 0.1) significantly reduced bacterial culturability under visible light. Transmission Electron Microscopy analysis revealed that nanoparticles with cobalt content caused bacteria to secrete biofilm, potentially offering some protection against the nanoparticles. CONCLUSION: ZnFe2O4 nanoparticles show the highest antibacterial effect amongst those tested. This is attributed to the combined action of Zn2+ ion release and the photocatalytic effect under visible light. Furthermore, Zn might inhibit protective biofilm secretion, leading to higher antibacterial effects.
Open Access
Effect of Cu substitution on the magnetic and magnetic induction heating response of CdFe₂O₄ spinel ferrite
(Elsevier, 2020) Ghasemi, R.; Echeverría Morrás, Jesús; Pérez de Landazábal Berganzo, José Ignacio; Beato López, Juan Jesús; Naseri, M.; Gómez Polo, Cristina; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Ciencias
In this work, a comparative study of the effect of Cu on the structural, magnetic and magnetic induction heating response in CdFe2O4 spinel is presented. The ceramic nanoparticles (Cu1−xCdxFe2O4; 0 ≤ x ≤ 1) were synthesized by co-precipitation from Cu(II), Cd(II) and Fe(III) salts. The samples, characterized by X-ray diffractometry, display the characteristic spinel cubic structure (space group Fm3m) where CdO is detected as main secondary phase (≈ 16% weight for x = 1). A high degree of nanoparticle agglomeration is inferred from the Transmission Electron Microscopy (TEM) images, as a consequence of the employed synthesis procedure. Regarding the magnetic properties, superparamagnetic behavior at room temperature can be disregarded according to the low field magnetization response (ZFC-FC curves). For 0.4 ≤ x ≤ 0.8 ratios, the samples display maximum values in the magnetic moment that should be correlated to the cation distribution between the octahedral and tetrahedral sites. Maximum magnetization values lead to an enhancement in the magnetic induction heating response characterized by highest heating temperatures under the action of an ac magnetic field. In particular, maximum SAR values are estimated for x = 0.8 as a combined effect of high magnetic moment, low dc coercive field (high susceptibility). Although these Cu-Cd ferrite nanoparticles display moderate SAR values (around 0.7 W/g), the control of the maximum heating temperatures through the cation distribution (composition) provides promising properties to be used as nanosized heating elements (i.e. hyperthermia agents).
Open Access
Modulating photocatalytic activity of nitrogen doped TiO2 nanoparticles via magnetic field
(Elsevier, 2024-07-30) Gómez Polo, Cristina; Cervera Gabalda, Laura María; Garayo Urabayen, Eneko; Beato López, Juan Jesús; Pérez de Landazábal Berganzo, José Ignacio; Ciencias; Zientziak; Institute for Advanced Materials and Mathematics - INAMAT2; Universidad Pública de Navarra / Nafarroako Unibertsitate Publikoa
The effect of the magnetic field on the photocatalytic activity of TiO2-based nanoparticles is analyzed using a magnetically-assisted photoreactor with permanent magnets to generate a controlled uniform magnetic field, B (¿82 mT). Nitrogen doped TiO2 nanoparticles (sizes around 10 nm) were synthesized through a solvothermal method employing Ti(IV) butoxide and HNO3 (x = 0, 0.5, 1, 1.5 and 2 mL) as precursors and their structural, optical and magnetic properties were analyzed. Specifically, nitrogen doping is confirmed through Hard X-ray Photoelectron Spectroscopy (HAXPES) in those samples synthesized with low HNO3 concentrations (x = 0.5, 1). The correlation between spin polarization (magnetic susceptibility) and visible photocatalytic activity (methyl orange as a model organic pollutant) is particularly analyzed. Surprisingly, opposite effects of the magnetic field on the photocatalytic performance are found in the visible range (above 400 nm) or under UV-Vis irradiation (decrease and increase in the photocatalytic activity, respectively, under magnetic field). The Langmuir-Hinshelwood model allows us to conclude that the strong decrease in adsorption under the magnetic field (around 42 % for x = 0.5) masks the increase in the kinetic constant (close to 58 % for x = 0.5) related mainly to the effect of Lorentz forces on the reduction of the electron-hole recombination.