Search Results (27)

Proton-conducting ceramics have gained significant attention in various applications. Yttrium-doped barium cerium zirconate (BaCe_xZr_1−x−yY_yO_3–δ) is the state-of-the-art proton-conducting electrolyte but poses a major challenge because of its high sintering temperature. Sintering aids have been found to substantially reduce the sintering temperature of BaCe_xZr_1−x−yY_yO_3–δ. This work evaluates, for the first time, the impact of NiO and ZnO addition in three different loadings (1, 3, 5 mol%), via wet mechanical mixing, on the sintering and electrical properties of a low cerium-containing composition, BaCe_0.2Zr_0.7Y_0.1O_3–δ (BCZY). The sintering temperature remarkably dropped from 1600 °C (for pure BCZY) to 1350 °C (for NiOBCZY and ZnOBCZY) while achieving > 95% densification. In general, ZnO gave higher densification than NiO, the highest being 99% for 5 mol% ZnOBCZY. Dilatometric studies revealed that ZnOBCZY attained complete shrinkage at temperatures lower than NiOBCZY. Up to 650 °C, ZnO showed higher conductivity compared to NiO for the same loading, mostly due to a higher extent of Zn incorporation inside the BCZY lattice as seen from the BCZY peak shift to a lower Bragg’s angle in X-ray diffractograms, and the bigger grain sizes of ZnO samples compared to NiO captured in scanning electron microscopy. At any temperature, the variation in conductivity as a function of sintering aid concentration followed the orders 1 mol% > 3 mol% > 5 mol% (for ZnO) and 1 mol% < 3 mol%~5 mol% (for NiO). This difference in conductivity trends has been attributed to the fact that Zn fully dissolves into the BCZY matrix, unlike NiO which mostly accumulates at the grain boundaries. At 600 °C, 1 mol% ZnOBCZY showed the highest conductivity of 5.02 mS/cm, which is, by far, higher than what has been reported in the literature for a Ce/Zr molar ratio <1. This makes ZnO a better sintering aid than NiO (in the range of 1 to 5 mol% addition) in terms of higher densification at a sintering temperature as low as 1350 °C, and higher conductivity. Full article

We investigated the thermoluminescence (TL) properties of Mn-doped zinc zirconate (ZnZrO₃:Mn) phosphors under beta (β) radiation. SEM revealed morphological changes with varying levels of Mn doping (0–5%), while XRD confirmed a pure cubic phase. Mn doping introduced luminescent centers, enhancing emission efficiency. Mn²⁺ ions facilitated green/red emissions (⁴T₁ → ⁶A₁), while Mn⁴⁺ contributed to deep-red emissions (²E → ⁴A₂), making the material suitable for optoelectronic applications. Compared to conventional phosphors, ZnZrO₃:Mn exhibited superior thermal stability, enhanced luminescence, and tunable emissions. The TL dose−response showed a systematic peak shift to higher temperatures with increasing radiation dose, confirming its potential for use in accurate dosimetry. The TL glow curves displayed primary (349 K) and secondary (473 K) peaks that were influenced by heating-rate variations, which led to peak shifts and increased intensity. An innovative thermal-cleaning approach (110–336 °C) refined luminescence by stabilizing deeper traps while erasing shallow-trap signals. This combined effect of Mn doping and thermal treatment optimized ZnZrO₃ phosphors’ structural, optical, and TL properties. These findings provide insights into their potential use in radiation dosimetry and display technologies, offering a new strategy for future perspective luminescent materials Full article

Thin films of zinc oxide (ZnO) doped with transition metals have recently gained significant attention due to their potential applications in a wide range of optoelectronic devices. This study focuses on ZnO thin films doped with the transition metals Co, Fe, and Zr, exploring various aspects of their structural, morphological, optical, electrical, and photoluminescence properties. The thin films were produced using RF and DC co-sputtering techniques. The X-ray diffraction (XRD) analysis revealed that all the doped ZnO thin films exhibited a stable wurtzite crystal structure, showcasing a higher structural stability compared to the undoped ZnO, while the atomic force microscopy (AFM) imaging highlighted a distinctive granular arrangement. Energy-dispersive X-ray spectroscopy was employed to confirm the presence of transition metals in the thin films, and Fourier-transform infrared spectroscopy (FTIR) was utilized to investigate the presence of chemical bonding. The optical characterizations indicated that doping induced changes in the optical properties of the thin films. Specifically, the doped ZnO thin film’s bandgap experienced a significant reduction, decreasing from 3.34 to 3.30 eV. The photoluminescence (PL) analysis revealed distinguishable emission peaks within the optical spectrum, attributed to electronic transitions occurring between different bands or between a band and an impurity. Furthermore, the introduction of these transition metals resulted in decreased resistivity and increased conductivity, indicating their positive influence on the electrical conductivity of the thin films. This suggests potential applications in solar cells and light-emitting devices. Full article

In this work, the results of ellipsometric studies of thin films of broadband oxides (ZnO, TiO₂, ZrO₂) and broadband oxides doped with Al₂O₃ (Al₂O₃–ZnO, Al₂O₃–TiO₂, Al₂O₃–ZrO₂) are presented. All layers have been produced using the atomic layer deposition method. Ellipsometric studies were performed in the wavelength range of 193–1690 nm. Sellmeier and Cauchy models were used to describe the optical properties of the tested layers. Dispersion dependencies of refractive indices were determined for thin layers of broadband oxides on silicon substrates, and then for layers of Al₂O₃ admixture. The EDX investigations enabled estimation of the composition of the alloys. The Bruggeman effective medium approximation (EMA) model was used to determine the theoretical dependencies of the dispersion refractive indices of the studied alloys. The refractive index values determined using the Bruggeman EMA model are in good agreement with the values determined from the ellipsometric measurements. The doping of thin layers of ZnO, ZrO₂ and TiO₂ with Al₂O₃ enables the creation of anti-reflective layers and filters with a specific refractive index. Full article

Although 4Ce4YSZ has high corrosion resistance, it faces challenges concerning its sinterability and ionic conductivity. Therefore, we studied destabilization behavior caused by corrosion and oxygen vacancy ordering according to ZnO doping. Powders of (4Ce4YSZ)_1−x(ZnO)_x (x = 0.5, 1, 2, 4 mol%) were synthesized using the sol-gel method. With the addition of ZnO, the cubic phase increased, and secondary phases were not observed. The (111) peak showed a higher angle shift in ZnO-doped 4Ce4YSZ compared to 4Ce4YSZ, and TEM-SAED revealed a reduction in the spacing of the (011)t plane, suggesting lattice contraction due to the substitution of the smaller Zn²⁺ (60 Å) for Zr⁴⁺ (84 Å) in the lattice. The local atomic structure analysis was conducted using EXAFS to investigate the oxygen vacancy ordering behavior. Zr K-edge Fourier transform data revealed a decrease in the Zr-O1 peak intensity with an increasing amount of ZnO doping, indicating an increase in oxygen vacancies. The Zr-O1 peak position shifted to the right, leading to an increase in the Zr-O1 interatomic distance. In the Y K-edge Fourier transform data, the Y-O1 peak intensity did not decrease, and there was little variation in the Y-O1 interatomic distance. These results suggest that the oxygen vacancies formed due to ZnO doping are located in the neighboring oxygen shell of Zn, rather than in the neighboring oxygen shells of Y and Zr. Impedance measurements were conducted to measure the conductivity, and as the amount of ZnO doping increased, the total conductivity increased, while the activation energy decreased. The increase in oxygen vacancies by ZnO doping contributed to the enhancement of conductivity, and it is considered that these created oxygen vacancies did not interact with Zn²⁺ and did not form defect associations. Fluoride-based molten salts were introduced to the specimens to assess the corrosion behavior in a molten salt environment. Yttrium depletion layers (YDLs) were formed on the surfaces of all specimens due to the leaching of yttrium. However, Ce remained relatively stable at the interface according to EDS line scans, suggesting a reduction in the phase transformation (cubic, tetragonal to monoclinic) typically associated with yttrium leaching in YSZ. Full article

Co-doped ZnO thin films have attracted much attention in the field of transparent conductive oxides (TCOs) in solar cells, displays, and other transparent electronics. Unlike conventional single-doped ZnO, co-doped ZnO utilizes two different dopant elements, offering enhanced electrical properties and more controllable optical properties, including transmittance and haze; however, most previous studies focused on the electrical properties, with less attention paid to obtaining high haze using co-doping. Here, we prepare high-haze Ga- and Zr-co-doped ZnO (GZO:Zr or ZGZO) using atmospheric pressure plasma jet (APPJ) systems. We conduct a detailed analysis to examine the interplay between Zr concentrations and film properties. UV-Vis spectroscopy shows a remarkable haze factor increase of 7.19% to 34.8% (+384%) for the films prepared with 2 at% Zr and 8 at% Ga precursor concentrations. EDS analysis reveals Zr accumulation on larger and smaller particles, while SIMS links particle abundance to impurity uptake and altered electrical properties. XPS identifies Zr mainly as ZrO₂ because of lattice stress from Zr doping, forming clusters at lattice boundaries and corroborating the SEM findings. Our work presents a new way to fabricate Ga- and Zr-co-doped ZnO for applications that require low electrical resistivity, high visible transparency, and high haze. Full article

This Special Issue includes 12 research papers on the development of various materials for adsorbing different contaminants in water, such as Sb, Cr(VI), Cu(II), Zn(II), fluorine, phenol, dyes (indigo carmine, Congo red, methylene blue, and crystal violet), and drugs (dlevofloxacin, captopril, and diclofenac, and paracetamol). The commercial, natural, and synthetic materials used as adsorbents comprise commercial activated carbon, natural clay and montmorillonite, biosorbent based on sugarcane bagasse or algal, graphene oxide, graphene oxide-based magnetic nanomaterial, mesoporous Zr-G-C₃N₄ nanomaterial, nitrogen-doped core–shell mesoporous carbonaceous nano-sphere, magnetic Fe-C-N composite, polyaniline-immobilized ZnO nanorod, and hydroxy-iron/acid–base-modified sepiolite composite. Various operational conditions are evaluated under batch adsorption experiments, such as pH, NaCl, solid/liquid ratio, stirring speed, contact time, solution temperature, initial adsorbate concentration. The re-usability of laden materials is evaluated through adsorption–desorption cycles. Adsorption kinetics, isotherm, thermodynamics, and mechanisms are studied and discussed. Machine learning processes and statistical physics models are also applied in the field of adsorption science and technology. Full article

Fabrication of ZnO nanoparticles (NPs) via green process has received enormous attention for its application in biomedicine. Here, a simple and cost-effective green route is reported for the synthesis of ZrO₂-doped ZnO/reduced graphene oxide nanocomposites (ZnO/ZrO₂/rGO NCs) exploiting ginger rhizome extract. Our aim was to improve the anticancer performance of ZnO/ZrO₂/rGO NCs without toxicity to normal cells. The preparation of pure ZnO NPs, ZnO/ZrO₂ NCs, and ZnO/ZrO₂/rGO NCs was confirmed by transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), photoluminescence (PL), and dynamic light scattering (DLS). XRD spectra of ZnO/ZrO₂/rGO NCs exhibited two distinct sets of diffraction peaks, ZnO wurtzite structure, and ZrO₂ phases (monoclinic + tetragonal). The SEM and TEM data show that ZrO₂-doped ZnO particles were uniformly distributed on rGO sheets with the excellent quality of lattice fringes without alterations. PL spectra intensity and particle size of ZnO decreased after ZrO₂-doping and rGO addition. DLS data demonstrated that green prepared samples show excellent colloidal stability in aqueous suspension. Biological results showed that ZnO/ZrO₂/rGO NCs display around 3.5-fold higher anticancer efficacy in human lung cancer (A549) and breast cancer (MCF7) cells than ZnO NPs. A mechanistic approach suggested that the anticancer response of ZnO/ZrO₂/rGO NCs was mediated via oxidative stress evident by the induction of the intracellular reactive oxygen species level and the reduction of the glutathione level. Moreover, green prepared nanostructures display good cytocompatibility in normal cell lines; human lung fibroblasts (IMR90) and breast epithelial (MCF10A) cells. However, the cytocompatibility of ZnO/ZrO₂/rGO NCs in normal cells was better than those of pure ZnO NPs and ZnO/ZrO₂ NCs. Augmented anticancer potential and improved cytocompatibility of ZnO/ZrO₂/rGO NCs was due to ginger extract mediated beneficial synergism between ZnO, ZrO₂, and rGO. This novel investigation emphasizes the significance of medicinal herb mediated ZnO-based NCs synthesis for biomedical research. Full article

Owing to its low resistivity, high transmittance, and tunable optical band gap, ZnO is of great interest for optoelectronic applications. Herein, the sol–gel technique was used to synthesize un-doped and zirconium-doped zinc oxide (ZZO) nanostructures with different concentrations of Zirconium (Zr). X-ray diffraction (XRD), scanning electron microscope (SEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), UV-Vis spectroscopy, and photoluminescence (PL) measurements were used to investigate the influence of Zr doping on the structural, optical, and electrical properties of developed nanostructures. XRD and SEM confirmed the increase in crystallite size with increasing concentrations of Zr. Raman analysis indicated the presence of oxygen vacancies in synthesized nanostructures. UV-Vis spectroscopy illustrated the blue shift of band gap and red shift of the absorption edge for ZZO nanostructures with increasing concentrations of Zr. For the measurement of electrical properties, the spin-coating technique was used to deposit un-doped and Zr-doped ZnO layers of ~165 nm thickness. The four-probe-point (4PP) method illustrated that the doping of Zr caused a reduction in electrical resistance. Hall Effect measurements showed a high value, 3.78 × 10²⁰ cm⁻³, of the carrier concentration and a low value, 10.2 cm²/Vs, of the carrier mobility for the Zr-doped layer. The high optical transmittance of ~80%, wide band gap of 3.51 eV, low electrical resistivity of 1.35 × 10⁻³ Ω·cm, and maximum carrier concentration of 3.78 × 10²⁰ cm⁻³ make ZZO nanostructures one of the most promising candidates for the application of transparent conductive oxide (TCO) in optoelectronic devices. Full article

The development of active, selective, and stable multicrystalline catalytic coatings on the inner surface of microcapillary reactors addresses environmental problems of fine organic synthesis, in particular by reducing the large quantities of reagents and byproducts. Thin-film nanosized bimetallic catalysts based on mesoporous pure titania and doped with zirconia, ceria, and zinc oxide, for use in microreactors, were developed, and the regularities of their formation were studied. The efficiency of PdZn/Ti_xM_1−xO_2±y (M = Ce, Zr, Zn) in the hydrogenation of 2-methyl-3-butyn 2-ol was studied with an emphasis on the stability of the catalyst during the reaction. The catalytic parameters depend on the adsorption properties and activity of PdZn and Pd(0) active centers. Under reaction conditions, resistance to the decomposition of PdZn is a factor that affects the stability of the catalyst. The zinc-doped coating proved to be the most selective and stable in the reaction of selective hydrogenation of acetylenic alcohols in a microcapillary reactor. This coating retained a high selectivity of 98.2% during long-term testing up to 168 h. Modification of the morphology and electronic structure of the active component, by doping titania with Ce and Zr, is accompanied by a decrease in stability. Full article

To achieve good long-term temperature stability in devices used in energy-conversion applications, this study is aimed at developing combined ceramics, referred to as PZN-PMN-PZT, comprising Pb(Zn_1/3Nb_2/3)O₃ (PZN) and Pb(Mn_1/3Nb_2/3)O₃ (PMN), which are typical relaxor ferroelectric materials, and Pb(Zr_,Ti)O₃ (PZT). The piezoelectric properties were compared based on several parameters according to the change in the composition ratio between relaxor materials, amounts of Sb₂O₃ dopant, and Zr/Ti ratio in the PZT system. Finally, we established optimal poling conditions to improve the electrical properties of the optimized piezoelectric material, based on the evaluation of ceramic properties according to the applied voltage during the poling process. The optimized composition of the investigated piezoelectric ceramics is represented by 0.14PZN-0.06PMN-0.80PbZr_0.49Ti_0.51 + 0.3 wt.% CuO + 0.3 wt.% Fe₂O₃ with 0.1 wt.% Sb₂O₃ doping, which yielded the superior properties (d₃₃ = 361 pC/N, Q_m = 1234, T_c = 306 °C). Full article

Proton-conducting solid–oxide fuel cell (H-SOFC) is an alternative promising low-temperature electrochemical cell for renewable energy, but the performance is insufficient because of the low activity of cathode materials at low temperatures. A layered perovskite oxide PrBaFe_1.9Zn_0.1O_5+δ (PBFZ) was synthesized and investigated as a promising cathode material for low-temperature H-SOFC. Here, the partial substitution of Fe by Zn further enhances the electrical conductivity and thermal compatibility of PrBaFe₂O_5+δ (PBF). The PBFZ exhibits improved conductivity in the air at intermediate temperatures and good chemical compatibility with electrolytes. The oxygen vacancy formed at the PBFZ lattice due to Zn doping enhances proton defects, resulting in an improved performance by extending the catalytic sites to the whole cathode area. A single cell with a Ni-BZCY anode, PBFZ cathode, and BaZr_0.7Ce_0.2Y_0.1O_3-δ (BZCY) electrolyte membrane was successfully fabricated and tested at 550–700 °C. The maximum power density and R_p were enhanced to 513 mW·cm⁻² and 0.3 Ω·cm² at 700 °C, respectively, due to Zn doping. Full article

Nowadays, durable protective coatings receive more attention in the field of conservation for several reasons (they are cost effective, time consuming, more resistance, etc.). Hence, this study was focused on producing a multi-functional, durable coating to protect different stone materials, especially, Lecce stone, bricks, and marble. For this purpose, ZrO₂-doped-ZnO-PDMS nanocomposites (PDMS, polydimethylsiloxane used as the binder) were synthesized by in situ reaction (doped nanoparticles were inserted into the polymer matrix during the synthesis of PDMS) and the performances of resulting coatings were examined by handling different experimental analyses. In particular, the study aimed to evaluate the durability properties of the coating along with the self-cleaning effect. As a result, the durability of the nanocomposite coating with respect to the well-known PDMS coating was assessed after exposure to two different ageing cycles: solar ageing (300 W, 1000 h) and humid chamber ageing (RH > 80%, T = 22 ± 3 °C, desiccator, 2 years). All the results were in good agreement with each other providing that newly prepared nanocomposite coating can be used as a durable protective coating for different stone materials. Full article

In the last decades photocatalysis has become one of the most employed technologies for the implementation of the so-called Advanced Oxidation Processes (AOPs) for the removal of harmful pollutants from wastewaters. The materials identified as the best photocatalysts are transition metal oxides, in which the band structure allows charge carrier separation upon solar irradiation. The photoinduced charge carrier can thus cause oxidative and reductive redox reactions at the surface, inducing the formation of the radical species able to initiate the AOPs. Despite the great advantages of this process (non-toxic, cheap and environmentally clean), the main drawback lies in the fact that the most efficient semiconductors are only able to absorb UV irradiation, which accounts for only 5% of the total solar irradiation at the Earth’s surface and not enough to generate the required amount of electron-hole pairs. On the other hand, many efforts have been devoted to the sensitization of wide band gap transition metal oxides to visible light, which represents a higher percentage (almost 45%) in the solar electromagnetic spectrum. Among all the strategies to sensitize transition metal oxides to visible irradiation, doping with lanthanides has been less explored. In this regard, lanthanides offer a unique electronic configuration, consisting in 4f orbitals shielded by a 5s5p external shell. This occurrence, coupled with the different occupation of the localized 4f orbitals would provide an astounding opportunity to tune these materials’ properties. In this review we will focus in depth on the modification of two promising photocatalytic transition metal oxides, namely ZnO and ZrO₂, with cerium, europium and erbium atoms. The aim of the work is to provide a comprehensive overview of the influence of lanthanides on the structural, optical and electronic properties of the modified materials, emphasizing the effect of the different 4f orbital occupation in the three considered doping atoms. Moreover, a large portion of the discussion will be devoted to the structural-properties relationships evidencing the improved light absorption working mechanism of each system and the resulting enhanced photocatalytic performance in the abatement of contaminants in aqueous environments. Full article

First-principles calculations based on density functional theory (DFT) were carried out to study the energetic stability and electronic properties of a bimetallic-doped α-Fe₂O₃ photoanode surface with (Zn, Ti) and (Zn, Zr) pairs for enhanced PEC water splitting. The doped systems showed negative formation energies under both O-rich and Fe-rich conditions which make them thermodynamically stable and possible to be synthesised. It is found that in a bimetallic (Zn, Ti)-doped system, at a doping concentration of 4.20% of Ti, the bandgap decreases from 2.1 eV to 1.80 eV without the formation of impurity states in the bandgap. This is favourable for increased photon absorption and efficient movement of charges from the valance band maximum (VBM) to the conduction band minimum (CBM). In addition, the CBM becomes wavy and delocalised, suggesting a decrease in the charge carrier mass, enabling electron–holes to successfully diffuse to the surface, where they are needed for water oxidation. Interestingly, with single doping of Zr at the third layer (L3) of Fe atoms of the {0001} α-Fe₂O₃ surface, impurity levels do not appear in the bandgap, at both concentrations of 2.10% and 4.20%. Furthermore, at 2.10% doping concentration of α-Fe₂O₃ with Zr, CBM becomes delocalised, suggesting improved carrier mobility, while the bandgap is altered from 2.1 eV to 1.73 eV, allowing more light absorption in the visible region. Moreover, the photocatalytic activities of Zr-doped hematite could be improved further by codoping it with Zn because Zr is capable of increasing the conductivity of hematite by the substitution of Fe³⁺ with Zr⁴⁺, while Zn can foster the surface reaction and reduce quick recombination of the electron–hole pairs. Full article