Search Results (632)

DFT calculations have been employed to investigate the impact of Sm dopant(s) on the structure and stability of periodic CeO₂(111) slab and Ce₁₄₀O₂₈₀ nanoparticle systems. We found that substituting Ce ion(s) with Sm ion(s) in the surface layer yields the most favorable doped configurations in both systems. Further, we evaluated how Sm ion(s) modify the reducibility of the systems—a key process in the catalytic applications of ceria. It has been found that a substantial reduction in oxygen vacancy formation energy occurs due to the presence of Sm ion(s), with values of 1.24 and 0.29 eV for mono- and bi-doped CeO₂(111), respectively, which are considerably lower than 2.43 eV obtained for the pristine ceria slab. As the system changes from slab to nanoparticle, mono-doping reduces this energy to 0.25 eV—about four times lower than that calculated for the pristine Ce₁₄₀O₂₈₀ nanoparticle. The presence of a second Sm ion within the nanoparticle leads to a dramatic decrease in E_vac, making the reduction process exothermic. In either slab or nanoparticle models, the Sm³⁺ ions prefer to be in close proximity to each other, and the formation of oxygen vacancies is most energetically favorable in the vicinity of Sm³⁺ ions. Full article

The increasing atmospheric CO₂ concentration is one of the major environmental challenges, necessitating not only emission reduction but also effective carbon utilization. Non-thermal plasma-catalytic CO₂ conversion offers an efficient pathway under mild conditions by synergistically combining plasma activation with catalytic surface reactions. In this study, mesoporous ceria catalysts were synthesized by different methods and characterized using N₂ adsorption–desorption, SEM, XRD, XPS, CO₂-TPD, and XRF techniques. The materials exhibited distinct textural and electronic properties, including variations in surface area, pore structure, and basicity. Plasma-catalytic CO₂ dissociation experiments were conducted in a dielectric barrier discharge reactor at near-room temperature. Among the synthesized catalysts, Ce(mp)-4 demonstrated the highest CO₂ conversion of 32.3% at a 5 kV input voltage and superior energy efficiency, which can be attributed to its meso-macroporous structure that promotes microdischarge formation and enhances CO₂ adsorption–desorption dynamics. CO was the only product obtained, with near-100% selectivity. Catalyst stability testing showed no deactivation while spent catalyst characterization indicated carbon-containing species. The findings in this study highlight the critical role of tailored pore structure and basic-site distribution in optimizing plasma-catalytic CO₂ dissociation performance, offering a promising strategy for energy-efficient CO₂ utilization. Full article

The activity of Co- and Ni-containing ceria-based catalysts for water–gas shift (WGS) reaction were examined in this work. The catalysts were prepared by the urea co-precipitation method. Sm and Pr dopant (5 wt.%) was used as a structural stabilizer of CeO₂, while Co or Ni was used in a small amount (1 wt.%). H₂-TPR experiments indicate that both Sm and Pr addition increased the reducibility of CeO₂. Among the studies’ catalysts, 1%Ni/Ce5%SmO exhibited the highest WGS activity. In addition, WGS rate was measured in the temperature range of 200–400 °C for Ni supported on CeO₂, Ce5%SmO, and Ce5%PrO. The activation energy of the reaction over 1%Ni/Ce5%SmO was 57 kJ/mol, while it was 61 and 66 kJ/mol, respectively, over 1%Ni/Ce5%PrO and 1%Ni/CeO₂ catalysts. A WGS reaction mechanism, CO adsorbed on the metal cluster is oxidized by oxygen supplied from the CeO₂ support at the metal–ceria interface. This oxygen is then re-oxidized by H₂O, which caps the oxygen vacancy on the ceria surface, and thereby oxygen vacancies serve as active sites for the WGS reaction. Raman experiments indicate that the presence of Sm in 1%Ni/Ce5%SmO catalyst promoted the formation of oxygen vacancies, leading to enhanced WGS performance. Full article

The aim of the presented work is to develop a more energy- and time-saving modification of a well-known hydrothermal synthesis method by reducing the time of the synthesis regime and drying step, as well as the possible removal of the calcination procedure. The structure and morphology of Gd-doped ceria (Ce_1−xGd_xO_2−x/2, where x = 0, 0.1, 0.2, 0.3, and 0.5), synthesized via the optimized hydrothermal method, were thoroughly investigated. Phase composition was analyzed using X-ray diffraction (XRD), while the structural units of the materials were identified by Fourier-transform infrared spectroscopy (FTIR). Chemical composition was studied using energy-dispersive X-ray spectroscopy (EDS) and further confirmed by energy-dispersive X-ray fluorescence (EDXRF). Transmission electron microscopy (TEM) was employed to analyze the size and shape of the nanoparticles. Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ce³⁺ ions in both doped and undoped CeO₂ samples. Full article

Antioxidant properties of inorganic nanoparticles in aqueous media are attracting growing interest due to their high surface reactivity. Materials such as cerium oxide, iron oxide, silver, and gold exhibit distinct radical-scavenging behaviors at the nanoscale, but reliable quantification remains challenging. Conventional assays developed for molecular antioxidants cannot be directly applied because probes such as 2,2-diphenyl-1-picrylhydrazyl (DPPH) require methanol–water mixtures and are unstable in aqueous nanoparticle suspensions, while other assays are affected by nanoparticle-induced absorption or fluorescence changes. Here we demonstrate strategies to correct these interferences by independently measuring nanoparticle optical properties after oxidation and customizing assay conditions to account for the dilute, per-particle concentrations of nanomaterials. Using a high-throughput 96-well format, four adapted assays revealed that silver, ceria, and iron oxide nanoparticles possess substantially higher antioxidant capacities than Trolox, while gold showed negligible activity. This optimized approach enables reproducible comparison of nanoparticle antioxidants and provides a platform for tailoring nanostructures with enhanced radical-scavenging properties. Full article

The development of cost-effective and highly sensitive hydrogen peroxide (H₂O₂) biosensors with robust stability is critical due to the pivotal role of H₂O₂ in biological processes and its broad utility across various applications. In this work, porous ceria hollow microspheres (CeO₂-phm) were synthesized using a solvothermal synthesis method and employed in the construction of an electrochemical biosensor for H₂O₂ detection. The resulting CeO₂-phm featured a uniform pore size centered at 3.4 nm and a high specific surface area of 168.6 m²/g. These structural attributes contribute to an increased number of active catalytic sites and promote efficient electrolyte penetration and charge transport, thereby enhancing its electrochemical sensing performance. When integrated into screen-printed carbon electrodes (CeO₂-phm/cMWCNTs/SPCE), the CeO₂-phm/cMWCNTs/SPCE-based biosensor exhibited a wide linear detection range from 0.5 to 450 μM, a low detection limit of 0.017 μM, and a high sensitivity of 2070.9 and 2161.6 μA·mM⁻¹·cm⁻²—surpassing the performance of many previously reported H₂O₂ sensors. In addition, the CeO₂-phm/cMWCNTs/SPCE-based biosensor possesses excellent anti-interference performance, repeatability, reproducibility, and stability. Its effectiveness was further validated through successful application in real sample analysis. Hence, CeO₂-phm with solvothermal synthesis has great potential applications as a sensing material for the quantitative determination of H₂O₂. Full article

This study presents a comprehensive characterization of monometallic (Co or Cu) and bimetallic (Co-Cu) catalysts supported on cerium oxide (CeO₂). XRD and TEM analyses revealed that crystallinity decreases after reduction and that metal dispersion is highly dependent on composition, with cobalt exhibiting greater dispersion than copper. The results confirmed a strong interaction between the metals and CeO₂, which alters the ceria structure and facilitates the reduction of the metal oxides. H₂-TPR and XPS data indicated that monometallic and the bimetallic 15Cu15Co catalysts achieved nearly complete reduction, whereas other bimetallic catalysts did not. Furthermore, CO chemisorption and H₂-TPD demonstrated that the hydrogen activation capacity correlates with the degree of catalyst reduction. Notably, bimetallic catalysts did not show enhanced hydrogen activation compared to their monometallic counterparts. This suggests that the dispersion and metal–support interaction are more critical factors for catalytic activity in this system than the formation of metal alloys. Although the furfural conversion was complete, the selectivity depended greatly on the catalyst composition. The 30Co_R catalyst was most selective for 1,5-pentanediol (38.4%), the 30Cu_R catalyst for 1,2-pentanediol (22.1%), and the bimetallic catalysts for THFA. Reutilising the 30Co_R catalyst after five catalytic cycles resulted in a gradual reduction in the selectivity of 1,5-pentanediol. Full article

This study investigates hyperpolishing of Zerodur^® substrates via chemical-mechanical polishing (CMP) using silica (SiO₂) and ceria (CeO₂) nanoparticles as controlled nano-abrasives. A pre-polishing stress-mirror stage was combined with systematic use of nanoparticles of variable size to evaluate surface-state evolution via optical rugosimeter, HRSEM, cross-sectional HRTEM, and XPS. A set of hexagonal mirrors with a circumscribed diameter of 30 mm was polished for one hour with each nanoparticle type. All tested slurries significantly improved surface quality, with both the smallest (37 nm) and largest (209 nm) SiO₂ particles achieving similar final roughness, though larger particles showed a slight performance advantage that could be offset by longer polishing with smaller particles. CeO₂ nanoparticles (30 nm) produced even better process efficiency and surface finishes than 37 nm SiO₂, demonstrating higher chemical-mechanical polishing efficiency with CeO₂. Sequential polishing strategies, first with 209 nm SiO₂, then with 37 nm SiO₂ and 30 nm CeO₂, also enhanced surface quality, confirming trends from single-particle trials. One of the most effective protocols was adapted and scaled up to 135 mm Zerodur^® mirrors with spherical and plano geometries, representative of precision optical components. The strategic approach adopted to achieve a high-quality surface finish in a reduced processing time relies on the sequential use of nanoparticles acting as complementary nano-abrasives. Indeed, applying two hours of polishing with 209 nm SiO₂ followed by two hours with 37 nm SiO₂ yielded exceptional results, with area roughness (Sa) values of 1 Å for spherical and 0.9 Å for plano surfaces. These results demonstrate the capability of nanoparticle-assisted CMP to produce sub-nanometric surface finishes and offer a robust, scalable approach for high-end optical manufacturing. Full article

The development of ceria (CeO_2−x)-based nanoantioxidants requires fine-tuning of structural and surface properties for enhancing antioxidant behavior in biological environments. In this contest, here ultrasmall water-dispersible CeO_2−x nanoparticles (NPs), characterized by a high Ce³⁺/Ce⁴⁺ ratio, were synthesized in a non-polar solvent and phase-transfer to an aqueous environment through ligand-exchange reactions using citric acid (CeO_2−x@Cit) and post-treatment with dopamine hydrochloride (CeO_2−x@Dopa). The concept behind this work is to enhance via surface engineering the intrinsic antioxidant properties of CeO_2−x NPs. For this purpose, thanks to electron transfer reactions between dopamine and CeO_2−x, the CeO_2−x@Dopa was obtained, characterized by increased surface Ce³⁺ sites and surface functionalized with polydopamine bearing o-quinone structures as demonstrated by complementary spectroscopic (UV–vis, FT-IR, and XPS) characterizations. To test the antioxidant properties of CeO_2−x NPs, the scavenging activity before and after dopamine treatment against artificial radical 1,1-diphenyl-2-picrylhydrazyl (DPPH^·) and the ability to reduce the reactive oxygen species in Diencephalic Immortalized Type Neural Cell line 1 were evaluated. CeO_2−x@Dopa demonstrated less efficiency in DPPH^· scavenging (%radical scavenging activity 13% versus 42% for CeO_2−x@Cit before dopamine treatment at 33 μM DPPH^· and 0.13 mg/mL loading of NPs), while it markedly reduced intracellular ROS levels (ROS production 35% compared to 66% of CeO_2−x@Cit before dopamine treatment with respect to control—p < 0.001 and p < 0.01, respectively). While steric hindrance from the dopamine-derived polymer layer limited direct electron transfer from CeO_2−x NP surface to DPPH^·, within cells the presence of o-quinone groups contributed with CeO_2−x NPs to break the autoxidation chain of organic substrates, enhancing the antioxidant activity. The functionalization of NPs with o-quinone structures represents a valuable approach to increase the inherent antioxidant properties of CeO_2−x NPs, enhancing their effectiveness in biological systems by promoting additional redox pathways. Full article

Ceria is an important redox catalyst due to the facile Ce³⁺/Ce⁴⁺ switching at its surface. Therefore, in situ determination of the oxidation state of surface cerium cations is of significant interest. Infrared spectroscopy of probe molecules such as CO holds great potential for this purpose. However, the ability of CO to reduce Ce⁴⁺ cations is an important drawback as it alters the initial cerium speciation. Dinitrogen (N₂), due to its chemical inertness, presents an attractive alternative. We recently demonstrated that low-temperature ¹⁵N₂ adsorption on stoichiometric ceria leads to the formation of complexes with Ce⁴⁺ cations on the (110) and (100) planes (bands at 2257 and 2252 cm⁻¹, respectively), while the (111) plane is inert. Here, we report results on the low-temperature ¹⁵N₂ adsorption on reduced ceria nanoshapes (cubes, polyhedra, and rods). A main band at 2255 cm⁻¹, with a weak shoulder at 2254 cm⁻¹, was observed. We attributed these bands to ¹⁵N₂ adsorbed on Ce³⁺ sites located on edges and corners as well as on {100} facets. In conclusion, ¹⁵N₂ adsorbs on the most acidic surface Ce³⁺ sites and enables their distinction from Ce⁴⁺ cations. Full article

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

Solar fuels production requires developing redox active materials with porous structures able to withstand thermochemical cycles with enhanced thermal stability under concentrated solar irradiation conditions. The mechanical performance of 3D-printed, macroporous black zirconia gyroid structures, coated with redox-active ceria, was assessed for their suitability in solar thermochemical cycles for CO₂ and H₂O splitting. Experiments were conducted using a 1.5 kW solar furnace to supply the high-temperature concentrated heat to a windowed reaction chamber to carry out thermal redox cycling under realistic on-sun conditions. The ceria coating on ceramic structures improved the thermal stability and redox efficiency while minimizing the quantity of the redox material involved. Crushing strength measurements showed that samples not directly exposed to the concentrated solar flux retained their mechanical performance after thermal cycling (~10 MPa), while those near the concentrated solar beam focus exhibited significant degradation due to thermal stresses and the formation of Ce_xZr_1−xO₂ solid solutions (~1.5 MPa). A Weibull modulus of 8.5 was estimated, marking the first report of such a parameter for fused filament fabrication (FFF)-manufactured black zirconia with gyroid architecture. Failure occurred via a damage accumulation mechanism at both micro- and macro-scales. These findings support the viability of ceria-coated cellular ceramics for scalable solar fuel production and highlight the need for optimized reactor designs. 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

The Ni/SiO₂ and the ceria-promoted Ni-CeO₂/SiO₂ were prepared by the impregnation method and co-impregnation method, respectively. The performance of the carbon dioxide reforming of methane (CDR) over Ni/SiO₂ and Ni-CeO₂/SiO₂ was investigated under the conditions of CH₄/CO₂ = 1.0, T = 800 °C, and GHSV = 60,000 mL·g⁻¹·h⁻¹. As a result, a high CDR performance, especially stability, was obtained over Ni-CeO₂/SiO₂, in which the conversion of CH₄ was very similar to that of the thermodynamic equilibrium (88%), and a negligible decrease in CH₄ conversion was observed after 50 h of the CDR reaction. Ni/SiO₂ and Ni-CeO₂/SiO₂ before and after the CDR reaction were subjected to structural characterization by XRD, TEM, TG–DSC, and physical adsorption. It was found that the addition of CeO₂ into Ni/SiO₂ significantly affected its surface area, the size and dispersion of Ni, the reduction behavior, and the coking properties. Moreover, the redox property of Ce³⁺-Ce⁴⁺, which accelerates the gasification of the coke, made Ni-CeO₂/SiO₂ successfully operate for 50 h without observable deactivation. Thus, the developed catalyst is very promising for the CDR. Full article

Electrochemical formation of ceria (mixed Ce₂O₃ and CeO₂) coatings on different types of screen-printed carbon electrodes (SPCEs) (based on graphite (C110), carbon nanotubes (CNT), single-walled carbon nanotubes (SWCNT), carbon nanofibers (CNF), and mesoporous carbon (MC)) were studied. Their potential applications as catalysts for various redox reactions and electrochemical sensors were investigated. The ceria oxide layers were electrodeposited on SPCEs at various current densities and deposition time. The morphology, structure, and chemical composition in the bulk of the ceria layers were studied by SEM and EDS methods. XRD was used to identify the formed phases. The concentration, chemical composition and chemical state of the elements on the surface of studied samples were characterized by XPS. It was established that the increase of the concentration of CeCl₃ in the solution and the cathode current density strongly affected the surface structure and concentration (relation between Ce³⁺ and Ce⁴⁺, respectively) in the formed ceria layers. At low concentration of CeCl₃ (0.1M) and low values of cathode current density (0.5 mA·cm⁻²), porous samples were obtained, while with their increase, the ceria coatings grew denser. Full article