Search Results (178)

This paper investigates the application of non-calcined metal tartrate as a novel alternative pore former to prepare functional ceramic composites to fabricate solid oxide fuel cells (SOFCs). Compared to carbonaceous pore formers, non-calcined pore formers offer high compatibility with various ceramic composites, providing better control over porosity and pore size distribution, which allows for enhanced gas diffusion, reactant transport and gaseous product release within the fuel cells’ functional layers. In this work, nanocrystalline gadolinium-doped ceria (GDC) and Ni-Gd-Ce-tartrate anode powders were prepared using a single-step co-precipitation synthesis method, based on the carboxylate route, utilising ammonium tartrate as a low-cost, environmentally friendly precipitant. The non-calcined Ni-Gd-Ce-tartrate was used to fabricate dense GDC electrolyte pellets (5–20 μm thick) integrated with a thin film of Ni-GDC anode with controlled porosity at 1300 °C. The dilatometry analysis showed the shrinkage anisotropy factor for the anode substrates prepared using 20 wt. The percentages of Ni-Gd-Ce-tartrate were 30 wt.% and 40 wt.%, with values of 0.98 and 1.01, respectively, showing a significant improvement in microstructural properties and pore size compared to those fabricated using a carbonaceous pore former. The results showed that the non-calcined pore formers can also lower the sintering temperature for GDC to below 1300 °C, saving energy and reducing thermal stresses on the materials. They can also help maintain optimal material properties during sintering, minimising the risk of unwanted chemical reactions or contamination. This flexibility enables the versatile designing and manufacturing of ceramic fuel cells with tailored compositions at a lower cost for large-scale applications. Full article

The use of CH₄ and CO₂ as fuels in direct internal reforming solid oxide fuel cells (DIR-SOFCs) is a promising strategy for efficient power generation with reduced greenhouse gas emissions. In this study, Ni catalysts supported on Ce–Pr mixed oxides with varying Pr contents (0–80 mol%) were synthesized, calcined at 1200 °C, and tested for dry reforming of methane (DRM), aiming at their application as catalytic layers in SOFC anodes. Physicochemical characterization (XRD, TPR, TEM) showed that increasing Pr loading enhances catalyst reducibility and promotes the formation of the Pr₂NiO₄ phase, which contributes to the generation of smaller Ni⁰ particles after reduction. Catalytic tests revealed that all samples exhibited low-carbon deposition, attributed to the large Ni crystallites. The catalyst with 80 mol% Pr showed the best performance, achieving the highest CH₄ conversion (72%), a H₂/CO molar ratio of 0.89, and improved stability. These findings suggest that Ni/Ce_0.2Pr_0.8 could be a promising candidate for use as a catalyst layer of anodes in DIR-SOFC anodes. Although electrochemical data are not yet available, future work will evaluate the catalyst’s performance and durability under SOFC-relevant conditions. Full article

Reconstruction of extensive bone defects due to age, trauma, or post-illness conditions remains challenging. Biomimetic scaffolds with osteogenic capabilities have been proposed as an alternative to the classical autograft and allograft implants. Three-dimensional scaffolds were obtained based on Ce-doped mesoporous bioactive glass (MBG) and Spongia agaricina (SA) as sacrificial templates functionalized with vitamin D₃. The study aimed to investigate the effect of vitamin D₃ functionalization on the optimal variant of a 3D scaffold doped with 3 mol% ceria, selected in our previous work based on its biological and physicochemical properties. Scanning electron microscopy (SEM) images of the non-functionalized/functionalized scaffolds revealed a porous structure with interconnected pores ranging from 100 to 350 μm. Fourier transform infrared spectroscopy (FTIR) and SEM analysis confirmed the surface functionalization. Cytotoxicity evaluation showed that all investigated scaffolds do not exhibit cytotoxicity and genotoxicity toward the Saos-2 osteosarcoma cell line. Moreover, the study demonstrated that functionalization with vitamin D₃ enhanced osteogenic activity in dental pulp stem cells (DPSCs) by increasing calcium deposition and osteocalcin secretion, as determined by Alizarin red stain and a colorimetric ELISA kit, as a result of its synergistic action with cerium ions. The results showed that the Ce-doped MBG scaffold functionalized with vitamin D₃ had the potential for applications in bone regeneration. Full article

With unique 4f electronic shells, rare earth metal-based catalysts have been attracting tremendous attention in electrocatalysis, including oxygen reduction reaction (ORR). In particular, atomically dispersed Ce/CeO₂-based catalysts have been explored extensively due to several unique features. This review article provides a comprehensive understanding of (i) the significance of the effect of Ce high-spin state on ORR activity enhancement on the Pt and non-pt electrocatalysts, (ii) the spatially confining and stabilizing effect of ceria on the generation of atomically dispersed transition metal-based catalysts, (iii) experimental and theoretical evidence of the effect of Ce³⁺ ↔ Ce⁴⁺ redox pain on radical scavenging, (iv) the effect of the Ce 4f electrons on the d-band center and electron transfer between Ce to the N-doped carbon and transition metal catalysts for enhanced ORR activity, and (v) the effect of Pt/CeO₂/carbon heterojunctions on the stability of the Pt/CeO₂/carbon electrocatalyst for ORR. Among several strategies of synthesizing Ce/CeO₂ electrocatalysts, the metal–organic framework (MOF)-derived catalysts are being perused extensively due to the tendency of Ce to readily coordinate with O- and N-containing ligands, which upon undergoing pyrolysis, results in the formation of high surface area, porous carbon networks with atomically dispersed metallic/clusters/nanoparticles of Ce active sites. This review paper provides an overview of recent advancements regarding Ce/CeO₂-based catalysts derived from the MOF precursor for ORR in fuel cells and metal–air battery applications and we conclude with insights into key issues and future development directions. Full article

In this work, the impact resistance of three zirconia ceramics was investigated: two yttria-stabilized zirconia (3Y-TZP and 1.5Y-TZP) and a ceria-stabilized-zirconia (Ce-TZP) composite. The impact resistance was evaluated through drop-ball impact tests on disk-shaped samples. The results are discussed in terms of the materials’ transformability, which was correlated to the size of tetragonal-to-monoclinic (t-m) transformation zones observed after the impact tests and to the volume fraction of the monoclinic content on fractured surfaces. The findings show that impact resistance increases with the ability of the material to undergo t-m transformation. The Ce-TZP composite exhibited the highest transformability and consequently the highest impact resistance, followed by 1.5Y-TZP, and then 3Y-TZP. Full article

Epitaxial layers of water-soluble Sr₃Al₂O₆ were fabricated as sacrificial layers on SrTiO₃ (100) single-crystal substrates using the Pulsed Laser Deposition technique. This approach envisages the possibility of developing a new generation of micro-Solid Oxide Fuel Cells and micro-Solid Oxide Electrochemical Cells for portable energy conversion and storage devices. The sacrificial layer technique offers a pathway to engineering free-standing membranes of electrolytes, cathodes, and anodes with total thicknesses on the order of a few nanometers. Furthermore, the ability to etch the SAO sacrificial layer and transfer ultra-thin oxide films from single-crystal substrates to silicon-based circuits opens possibilities for creating a novel class of mixed electronic and ionic devices with unexplored potential. In this work, we report the growth mechanism and structural characterization of the SAO sacrificial layer. Epitaxial samarium-doped ceria films, grown on SrTiO3 substrates using Sr₃Al₂O₆ as a buffer layer, were successfully transferred onto silicon wafers. This demonstration highlights the potential of the sacrificial layer method for integrating high-quality oxide thin films into advanced device architectures, bridging the gap between oxide materials and silicon-based technologies. Full article

Hydrogen is a priority energy vector for energy transition. Its production from renewable feedstock like ethanol is suitable for many applications. The performance of a Ni catalyst supported on samaria-doped ceria in the production of hydrogen by the reforming of ethanol is investigated, adding Sm₂O₃ to CeO₂ in molar ratios of 1:9, 2:8, and 3:7. A CeO₂-supported Ni catalyst was also evaluated for comparative purposes. The supports were prepared by the coprecipitation method and Ni was incorporated by incipient wetness impregnation to obtain catalysts with a Ni/(Ce+Sm) molar ratio of 4/6. The catalysts were characterized by a nitrogen adsorption isotherm, X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Increasing Sm₂O₃ content leads to a more homogeneous distribution of Sm₂O₃ and Ni particles on the support, and higher oxygen mobility, favoring the catalytic properties. The catalyst with a Sm₂O₃/CeO₂ molar ratio of 3/7 showed outstanding behavior, with an average ethanol conversion of 97%, hydrogen yield of 68%, and great stability. The results suggest that the main route for hydrogen production is ethanol dehydrogenation, followed by steam reforming of acetaldehyde, and acetone and ethylene formation are promoted by increasing Sm content in the outer surface of the catalyst. Full article

Developing efficient strategies for VOC emission abatement is an urgent task for protection of the environment and human health. Complete catalytic oxidation exhibits advantages, making it an effective, environmentally friendly, and economically profitable approach for VOC elimination. Pd-based catalysts are known as highly active for hydrocarbon catalytic oxidation. The nature of carrier materials is of particular importance because it may affect activity by changing physicochemical properties of the palladium species. In this work, Al₂O₃, CeO₂, CeO₂-Al₂O₃, and Y-doped CeO₂-Al₂O₃ were used as carriers of palladium catalysts. Methane and benzene were selected as representatives of two types of hydrocarbons. A decisive step in complete methane oxidation is the first C–H bond breaking, while the extraordinary stability of the six-membered ring structure is a challenge in benzene oxidation. The support effect was explored by textural measurements using XRF, XRD, XPS, EPR, and TPR techniques. Three ceria-containing samples showed superior CH₄ oxidation performance, achieving 90% methane conversion at about 300 °C and complete oxidation at 320 °C. Evidence for presence of Pd²⁺ species in all samples regarded as most active was provided by XP-derived analysis. Pd/Y-Ce/Al catalysts exhibited very high activity in benzene oxidation by reaching 100% conversion at 180 °C. The contributions of higher Pd and Ce³⁺ surface concentrations, the presence of O₂⁻-adsorbed superoxo species, and Pd⁰ ↔ PdO redox transfer were considered. The potential of a simple, environmentally friendly, and less energy demanding mechanochemical preparation procedure of mixed oxides was demonstrated. Full article

How important is the support during the rational design of a catalyst? Herein, doped ceria (Zr; Pr and Tb) was used as an active support to prepare Pt catalysts (0.5 wt%) for glycerol selective oxidation. A thorough characterization of achieved catalytic systems showed that the nature of doping elements led to different physicochemical properties. The presence of surface Pr³⁺ and Tb³⁺ not only increased oxygen vacancies but also electron mobility, modifying the oxidation state of platinum particles. The redox properties of the catalyst were also affected, achieving a close interaction between the support and metal particles even in the form of Pt-O-Pr(Tb) solid solutions. Furthermore, the combination of medium-sized metal particle dispersion, strong metal–support interaction and a synergy between the amount of oxygen vacancies and Pt⁰, observed in the Pt/CeTb catalyst, led to a high turnover frequency (TOF) and increased selectivity to glyceric acid. Thus, the present study reveals how a simple structural modification of active supports, such as cerium oxide, by means of doping elements is capable of improving the catalytic performance during glycerol selective oxidation, avoiding the cumbersome methods of synthesis and activation treatments. Full article

Thin films of gadolinium-doped ceria (GDC) nanoparticles were fabricated as electrolytes for low-temperature solid oxide fuel cells (SOFCs) by combining electrophoretic deposition (EPD) and the successive ionic layer adsorption and reaction-air spray plus (SILAR-A+) method. The Ce_1−xGd_xO_2−x/2 solid solution was synthesized using hydrothermal (HY) and solid-state (SS) procedures to produce high-quality GDC nanoparticles suitable for EPD fabrication. The crystalline structure, cell parameters, and phases of the GDC products were analyzed using X-ray diffraction. Variations in oxygen vacancy concentrations in the GDC samples were achieved through the two synthetic methods. The ionic conductivities of pressed pellets from the HY, SS, and commercial G_0.2DC samples, measured at 150 °C, were 0.6 × 10⁻⁶, 2.6 × 10⁻⁶, and 2.9 × 10⁻⁶ S/cm, respectively. These values were determined using electrochemical impedance spectroscopy (EIS) with a simplified equivalent circuit method. The morphologies of G_0.2DC thin films prepared via EPD and SILAR-A+ processes were characterized, with particular attention to surface cracking. Crack-free GDC thin films, approximately 730–1200 nm thick, were successfully fabricated on conductive substrates through the hybridization of EPD and SILAR-A+, followed by hydrothermal annealing. EIS and ionic conductivity (1.39 × 10⁻⁹ S/cm) measurements of the G_0.2DC thin films with thicknesses of 733 nm were performed at 300 °C. Full article

A single-bed and dual-bed catalyst system was studied to maximize H₂ production from the combination of partial oxidation of CH₄ and water gas shift reaction. In addition, the different types of catalysts, including Ni, Cu, Ni-Re, and Cu-Re supported on gadolinium-doped ceria (GDC) were investigated under different operating conditions of temperature (400–650 °C). Over Ni-based catalysts, methane can easily dissociate on a Ni surface to give hydrogen and carbon species. Then, carbon species react with lattice oxygen of ceria-based material to form CO. The addition of Re to Ni/GDC enhances CH₄ dissociation on the Ni surface and increases oxygen storage capacity in the catalyst, thus promoting carbon elimination. In addition, the results showed that a dual-bed catalyst system exhibited catalytic activity better than a single-bed catalyst system. The dual-bed catalyst system, by the combination of 1%Re4%Ni/GDC as a partial oxidation catalyst and 1%Re4%Cu/GDC as a water gas shift catalyst, provided the highest CH₄ conversion and H₂ yield. An addition of Re onto Ni/GDC and Cu/GDC caused an increase in catalytic performance because Re addition could improve the catalyst reducibility and increase metal surface area, as more of their surface active sites are exposed to reactants. Full article

Increasing the concentration of oxygen vacancies in ceria-based materials to solve the bottleneck of their applications in various fields has always been a research hotspot. In this paper, ceria-based cerium–oxygen–sulfur (Ce-O-S) composites that were composed of CeO₂, Ce₄O₄S₃, and Ce₂(SO₄)₃ were synthesized by a precipitation method. The compositional, structural, morphological, and light response characteristics of prepared Ce-O-S composites were investigated by various characterization techniques. The molar ratio of oxygen vacancies to lattice oxygen can reach a maximum of 1.83 with Ce-O-S composites. The band gap values of the Ce-O-S composites were less than 3.00 eV, and the minimum value was 2.89 eV (at pH 12), which successfully extended the light response range from the ultraviolet light region to the short-wave blue light region. The remarkable light response performance of Ce-O-S composites can be mainly attributed to the high proportion of oxygen vacancy. Moreover, the higher proportion of oxygen vacancies can be attributed to the doping of Ce (+3) and S (−2) in the lattice of CeO₂, and the synergistic effect of CeO₂, Ce₄O₄S₃, and Ce₂(SO₄)₃. Moreover, the ceria-based Ce-O-S composites with rich oxygen vacancy in this research can be applied in light blocking, photocatalysis, and other related fields. Full article

The water–gas shift (WGS) reaction is one of the most significant reactions in hydrogen technology since it can be used directly to produce hydrogen from the reaction of CO and water; it is also a side reaction taking place in the hydrocarbon reforming processes, determining their selectivity towards H₂ production. The development of highly active WGS catalysts, especially at temperatures below ~450 °C, where the reaction is thermodynamically favored but kinetically limited, remains a challenge. From a fundamental point of view, the reaction mechanism is still unclear. Since specific nanoshapes of CeO₂-based supports have recently been shown to play an important role in the performance of metal nanoparticles dispersed on their surface, in this study, a comparative study of the WGS is conducted on Pt nanoparticles dispersed (with low loading, 0.5 wt.% Pt) on CeO₂ and gadolinium-doped ceria (GDC) supports of different nano-morphologies, i.e., nanorods (NRs) and irregularly faceted particle (IRFP) CeO₂ and GDC, produced by employing hydrothermal and (co-)precipitation synthesis methods, respectively. The results showed that the support’s shape strongly affected its physicochemical properties and in turn the WGS performance of the dispersed Pt nanoparticles. Nanorod-shaped CeO_2,NRs and GDC_NRs supports presented a higher specific surface area, lower primary crystallite size and enhanced reducibility at lower temperatures compared to the corresponding irregular faceted CeO_2,IRFP and GDC_IRFP supports, leading to up to 5-fold higher WGS activity of the Pt particles supported on them. The Pt/GDC_NRs catalyst outperformed all other catalysts and exhibited excellent time-on-stream (TOS) stability. A variety of techniques, namely N₂ physical adsorption–desorption (the BET method), scanning and transmission electron microscopies (SEM and TEM), powder X-ray diffraction (PXRD) and hydrogen temperature programmed reduction (H₂-TPR), were used to identify the texture, structure, morphology and other physical properties of the materials, which together with the in situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) and detailed kinetic studies helped to decipher their catalytic behavior. The enhanced metal–support interactions of Pt nanoparticles with the nanorod-shaped CeO_2,NRs and GDC_NRs supports due to the creation of more active sites at the metal–support interface, leading to significantly improved reducibility of these catalysts, were concluded to be the critical factor for their superior WGS activity. Both the redox and associative reaction mechanisms proposed for WGS in the literature were found to contribute to the reaction pathway. Full article

Catalytic activity, mechanisms, and active sites were determined for methane steam reforming (MSR) over gadolinium-doped ceria (GDC) supported iridium (0.1 wt%) prepared by impregnation of GDC with iridium acetylacetonate. Isothermal steady-state rate measurements followed by micro-gas chromatography analysis were performed at 660 and 760 °C over Ir/GDC samples pretreated in N₂ or H₂ at 900 °C. Transient responses to CH₄ or H₂O step changes in isothermal conditions were carried out at 750 °C over Ir/GDC pretreated in He or H₂ using online quadrupole mass spectrometry. In the proposed mechanism, Ir/GDC proceeds through a dual-type active site associating, as follows: (i) Ir metallic particles surface as active sites for the cracking of CH₄ into reactive C species, and (ii) reducible (Ce⁴⁺) sites at GDC surface responsible for a redox mechanism involving Ce⁴⁺/Ce³⁺ sites, being reduced by reaction with reactive C into CO (or CO₂) depending on the oxidation state of GDC and re-oxidized by H₂O. Full reduction of reducible oxygen species is possible with CH₄ after He treatment, whereas only 80% is reached in CH₄ after H₂ treatment. Full article

In this study, 12 mol% ceria-stabilized tetragonal zirconia polycrystal ceramics with xNd₂O₃ (where x equals 0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.7) were synthesized via the solid-state method, and the effects of Nd₂O₃ doping amounts on the mechanical properties and microstructure were studied. The results show that with an increase in the Nd₂O₃ doping amount, the grain size of the ceramics was reduced from 2.93 μm to 0.69 μm. The hardness and strength of the ceramics increased significantly, while the fracture toughness decreased. The reduction in fracture toughness was attributed to the reduction in tetragonal grain size, which suppressed the tetragonal–monoclinic phase transformation caused by stress. Additionally, as the content of Nd₂O₃ increased, the formation of cubic zirconia accelerated, but no second phase was observed. Most importantly, when the doping amount of Nd₂O₃ reached 0.3 mol%, the comprehensive mechanical characteristics of the ceramics were optimal. This provides a research basis for the preparation of nanoscale 12 mol% ceria-stabilized tetragonal zirconia polycrystal ceramics. Full article