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Methanol is a promising hydrogen carrier for fuel cell vehicles (FCVs) via methanol steam reforming (MSR) reaction. Ceria supported copper catalyst has attracted extensive attentions due to the extraordinary oxygen storage capacity and abundant oxygen vacancies. Herein, we developed a colloidal solution combustion (CSC) method to synthesize a porous Cu/CeO2(CSC) catalyst. Compared with Cu/CeO2 catalysts prepared by other methods, the Cu/CeO2(CSC) catalyst possesses highly dispersed copper species and abundant Cu+-Ov-Ce3+ sites at the copper-ceria interface, contributing to methanol conversion of 66.3 %, CO2 selectivity of 99.2 %, and outstanding hydrogen production rate of 490 mmol gcat-1 h-1 under 250 °C. The linear correlation between TOF values and Cu+-Ov-Ce3+ sites amount indicates the vital role of Cu+-Ov-Ce3+ sites in MSR reaction, presenting efficient ability in activation of water. Subsequently, a deep understanding of CSC method is further presented. In addition to serving as a hard template, the colloidal silica also acts as disperser between nanoparticles, enhancing the copper-ceria interactions and facilitating the generation of Cu+-Ov-Ce3+ sites. This study offers an alternative approach to synthesize highly dispersed supported copper catalysts.
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Currently, numerous bone tumor patients undergo tumor recurrence after surgical resection, which seriously affects their quality of life. In this study, the ceria (CeO2) nanoparticle was added to Poly-L-Lactic Acid (PLLA) bone implants endowing the bone implant with antitumor function. The results showed that the reactive oxygen species increased in U2OS cells while it dropped in HEK293 cells as the CeO2 content increased. Meanwhile, the PLLA-8CeO2 showed a high cell inhibition rate of 53.66 % for U2OS cells and possessed a high cell viability of 76.96 ± 2.20 % for HEK293 cells, meaning that the implant could kill bone tumor cells meanwhile show good cytocompatibility for normal cells. These were mainly due to the fact that the CeO2 nanoparticles acted as a superoxide dismutase in tumor cells reducing superoxide to hydrogen peroxide, inducing an increase in reactive oxygen species levels. The excess reactive oxygen species could result in tumor cell apoptosis by disrupting mitochondrial structure, oxidizing proteins, and promoting DNA denaturation. Moreover, the compressive strength of PLLA was improved by the CeO2 addition due to its particle dispersion strengthening. Besides, the PLLA-CeO2 had a faster degradation rate compared to PLLA. Overall, the PLLA-CeO2 is a promising implant material for bone tumor treatment.
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A lanthanum-cerium-based abrasive composed of CeO2, LaOF, and LaF3 was commercially obtained. The effect of sodium hexametaphosphate (SHMP) on powder dispersion behavior was systematically investigated using the combined techniques of liquid contact angle, turbidity, zeta potential (ZP), scanning electron microscopy (SEM), powder X-ray diffraction (XRD) combined with Rietveld refinements, X-ray photoelectron spectroscopy (XPS), and polishing tests. The results indicated that the addition of 0.5 wt.% SHMP dispersant to the 5 wt.% lanthanum-cerium-based slurry produced the most stable suspension with a high turbidity of 2715 NTU and a low wetting angle of 45°. The as-obtained slurry displayed good surface polishing quality for K9 glass, with low surface roughness (Ra) of 0.642 and 0.515 nm (in the range of 979 × 979 µm2) at pH = 6 and 11, respectively, which corresponds to the fact that it has local maximum absolute values of ZP at these two pH values. SEM images demonstrated that after appropriate grafting of SHMP, the particle aggregation was reduced and the slurry's dispersion stability was improved. In addition, the dispersion mechanism was explained based on the principle of complexation reaction, which reveals that the dispersant SHMP can increase the interparticle steric hindrance and electrostatic repulsions. In an acidic environment, steric hindrance dominates, while electrostatic repulsion prevails under alkaline conditions. As expected, this polishing slurry may find potential applications in manufacturing optical devices and integrated circuits.
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Tungsten-modified CeO2 is an excellent catalyst for the catalytic conversion of ammonia. However, the geometric and electronic properties of this catalyst and the detailed reaction mechanisms are not well understood. In this work, the potential configurations of various monomer tungsten oxides supported on the CeO2(111) surface (WOX(x = 0-4)/CeO2(111)) are systematically studied and their relative stabilities are evaluated by using on-site Coulomb interaction corrected density functional theory calculations. Their performances are also investigated in enhancing the catalytic efficiency of NH3 adsorption and activation. It is found that the WOx clusters can always form tetrahedron-like structures on the CeO2(111) surface, and the CeO2(111) can exhibit both oxygen- and electron-storage roles to help the WOX maintain such tetrahedron-like WO4 structures and keep the W species at the highest 6+ state. Moreover, the flexibility of the tetrahedral WO4 structure leads to the preferential heterolytic NH3 dissociation at the WO sites, forming stable WNH2 and OH species. This study deepens the understanding of the unique oxygen- and electron-storage effects of the CeO2 support, it also provides valuable insights into the extraordinary catalytic properties of the W-modified CeO2 in NH3 conversion, paving the way for the rational design of more efficient CeO2-based NH3 treatment catalysts.
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Transmission electron microscopy (TEM) plays a crucial role in heterogeneous catalysis for assessing the size distribution of supported metal nanoparticles. Typically, nanoparticle size is quantified by measuring the diameter under the assumption of spherical geometry, a simplification that limits the precision needed for advancing synthesis-structure-performance relationships. Currently, there is a lack of techniques that can reliably extract more meaningful information from atomically resolved TEM images, like nuclearity or geometry. Here, cycle-consistent generative adversarial networks (CycleGANs) are explored to bridge experimental and simulated images, directly linking experimental observations with information from their underlying atomic structure. Using the versatile Pt/CeO2 (Pt particles centered ≈2 nm) catalyst synthesized by impregnation, large datasets of experimental scanning transmission electron micrographs and physical image simulations are created to train a CycleGAN. A subsequent size-estimation network is developed to determine the nuclearity of imaged nanoparticles, providing plausible estimates for ≈70% of experimentally observed particles. This automatic approach enables precise size determination of supported nanoparticle-based catalysts overcoming crystal orientation limitations of conventional techniques, promising high accuracy with sufficient training data. Tools like this are envisioned to be of great use in designing and characterizing catalytic materials with improved atomic precision.
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Posterior uveitis is a leading cause of vision impairment and blindness globally due to its detrimental effects on the choroid and retina. The condition is worsened by oxidative stress, which heightens inflammation and perpetuates a cycle of damage that current treatments only temporarily relieve. To address this, a novel treatment involving the in situ crystallization of ultrasmall cerium oxide nanoparticles (≈3 nm) on mesenchymal stem cell (MSC) extracellular vesicles (EVs) for the management of primed mycobacterial uveitis (PMU) is developed. This nanohybrid leverages the individual and synergistic effects of its components for a comprehensive therapeutic approach. The cerium oxide nanoparticles act as a nanozyme to reduce inflammation and scavenge excessive reactive oxygen species (ROS), while the MSC EVs, with their biocompatibility, modulate inflammatory cell infiltration and alleviate tissue damage. This synergistic system offers a promising new treatment strategy for ocular diseases characterized by oxidative stress and inflammation.
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The mononuclear phagocytic system clears the circulating inorganic nanomaterials from the bloodstream, which raises concerns about the chronic toxicity of the accumulated metal species. A better understanding of the behavior of each metal after systemic injection is thus required for clinical translations. This study investigates the significance of the metal-ligand interaction on the accumulation of cerium and demonstrates that only the form in which cerium is coordinated to a multidentate chelator with a strong binding affinity does not accumulate in major organs. Specifically, cerium complexed with diethylenetriamine pentaacetic acid (DTPA) forms renally excretable nanoparticles in vivo to circumvent the leaching of cerium ions, whereas weakly coordinated cerium-based nanomaterials produce insoluble precipitates upon encountering physiological phosphate anions. Ceria-based renally clearable nanoparticles (CRNs) derived from cerium-DTPA are utilized as the antioxidant pair with iron-DTPA, in which their combination leverages the Fenton reaction to synergistically scavenge hydrogen peroxide. This reduces the gene expression of pro-inflammatory factors in the macrophages activated with lipopolysaccharide as well as improves the survival rate of septic mice by alleviating the systemic inflammatory response and its downstream tissue injury in the liver, spleen, and kidneys. This study demonstrates that CRNs combined with iron-DTPA can be utilized as nonaccumulative nanomedicines for treating systemic inflammation, thereby overcoming the limitations of conventional ceria nanoparticle-based treatments.
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Antioxidantes , Cerio , Hierro , Sepsis , Cerio/química , Cerio/farmacología , Animales , Ratones , Antioxidantes/química , Antioxidantes/farmacología , Sepsis/tratamiento farmacológico , Sepsis/metabolismo , Hierro/química , Hierro/metabolismo , Riñón/metabolismo , Riñón/efectos de los fármacos , Riñón/patología , Células RAW 264.7 , Ácido Pentético/química , Nanopartículas/química , Lipopolisacáridos/farmacologíaRESUMEN
Redox reactions on the surface of transition metal oxides are of broad interest in thermo, photo, and electrocatalysis. H2 temperature-programmed reduction (H2-TPR) is commonly used to probe oxide reducibility by measuring the rate of H2 consumption during temperature ramps, assuming that this rate is controlled by oxide reduction. However, oxide reduction involves several elementary steps, such as H2 dissociation and H-spillover, before surface reduction and H2O formation occur. In this study, we evaluated the kinetics of H2 consumption over CeO2 and Pt/CeO2 with varying Pt loadings and structures to identify the elementary steps probed by H2-TPR. Literature often attributes changes in H2-TPR characteristics with Pt addition to increased CeO2 reducibility. However, our analysis revealed that the H2 consumption rate is measurement of the rate of H-spillover at Pt-CeO2 interfaces and is determined by the concentration of Pt species on Pt nanoclusters that dissociate H2. Therefore, lower temperature H2 consumption observed with Pt addition does not indicate higher CeO2 reducibility. Measurements on samples with mixtures of Pt single-atoms and nanoclusters demonstrated that H2-TPR can effectively quantify dilute Pt nanocluster concentrations, suggesting caution in directly linking H2-TPR characteristics to oxide reducibility while highlighting alternative material insights that can be gleaned.
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Utilizing rare earth doped ceria in solid oxide cells (SOCs) engineering is indeed a strategy aimed at enhancing the electrochemical devices' durability and activity. Particularly, Gd-doped ceria (GDC) is actively used for barrier layer and catalytic additives in solid oxide fuel cells (SOFCs). In this study, experiments are conducted with La-doped CeO2 (LDC), in which the Ce sites are predominantly occupied by La, to prevent the formation of the Ce-Zr solid solution. This LDC is comparably used as a functional interlayer between the electrolyte and cathode if sintered at lower temperatures to avoid La2Zr2O7 impurity. In addition, the high substitution of La3+ into the ceria lattice improves the oxygen non-stoichiometry of LDC, leading to accelerated electrochemical high performance by the additional role of LDC for oxygen supplier capacitance at high current operation. Thus, it is confirmed that the improved SOFC high performance is achieved at the maximum power density (MPD) of ≈2.15 W cm-2 at 800 °C when the optimized LDC buffer layer is hired at the anode-supported typed-Samsung's SOFC by lowering the sintering temperature to prevent LDC's impurity reaction.
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In this work, non-ordered and ordered CeO2-based catalysts are proposed for CO2 conversion to dimethyl carbonate (DMC). Particularly, non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635-722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation method (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase as follows: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activities for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield is found for the CeO2@SBA-15_TS nanocomposite. This finding can presumably be ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, leading to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants.
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Ferroionic materials combine ferroelectric properties and spontaneous polarization with ionic phenomena of fast charge recombination and electrodic functionalities. In this paper, we propose the concept of tunable polarization in CeO2-δ (ceria) thin (5 nm) films induced by built-in remnant polarization of a BaTiO3 (BTO) ferroelectric thin film interface, which is buried under the ceria layer. Upward and downward fixed polarizations at the BTO thin film (10 nm) are achieved by the lattice termination engineering of the SrO or TiO2 terminated Nb:SrTiO3 (NSTO or STN) substrate. We find that the ceria layer punctually replicates the polarization of the BTO interface via a dynamic reconfiguration of its intrinsic defects, i.e., oxygen vacancies and small polarons. Tunable oxidative or reducing properties (redox) also arise at the surface from the built-in polarization. Opposite polarities at the ceria termination tune the chemo-physical dynamics toward water molecule adsorbates. The inversion of the surface potential leads to a modulation of the water adsorption-desorption equilibrium and water ionization (splitting) redox overpotentials within ±400 mV at room temperature, depending on the ceria termination's charges. Such tunability opens up the perspectives of using ferroionics for wireless electrochemically enhanced catalysis.
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Ceria-based nanoparticles are versatile in treating various inflammatory diseases, but their feasibility in clinical translation is undermined by safety concerns and a limited delivery system. Meanwhile, the idiopathic nature of inflammatory bowel disease (IBD) calls for a wider variety of therapeutics via moderation of the intestinal immune system. In this regard, the synthesis and oral formulation of iron-ceria nanoparticles (CF NPs) with enhanced nanozymic activity and lower toxicity risk than conventional ceria-based nanoparticles are reported. CF NPs are clustered in calcium phosphate (CaP) and coated with a pH-responsive polymer to provide the enteric formulation of iron-ceria nanotablets (CFNT). CFNT exhibits a marked alleviative efficacy in the dextran sodium sulfate (DSS)-induced enterocolitis model in vivo by modulating the pro-inflammatory behavior of innate immune cells including macrophages and neutrophils, promoting anti-inflammatory cytokine profiles, and downregulating key transcription factors of inflammatory pathways.
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Metal-supported solid oxide fuel cell (MS-SOFC) is very promising for intermediate temperature solid oxide fuel cell (SOFC) due to better mechanical strength, low materials cost, and simplified stack assembling. However, the effects of metal support on the performance and temperature field of MS-SOFC is still necessary for further study. In this study, a three-dimensional multi-physical model is developed to investigate how the use of metal support influence the electrochemical performance and the temperature field of MS-SOFC with a ceria-based electrolyte. The multi-physical model fully considers the conservation equations of mass, momentum, and energy that are coupled with mass transport and electrochemical reactions. The wall temperature in the radiation model is calculated using a discrete method. It is found that the radiation heat flux accounts for 3.13 % of the total heat flux. More importantly, the temperature difference of MS-SOFC is 3.61 % lower than that of conventional anode-supported SOFC, leading to improved temperature uniformity and cell durability.
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Electrochemical carbon dioxide reduction (ECO2RR) shows great potential to create high-value carbon-based chemicals, while designing advanced catalysts at the atomic level remains challenging. The ECO2RR performance is largely dependent on the catalyst microelectronic structure that can be effectively modulated through surface defect engineering. Here, we provide an atmosphere-assisted low-temperature calcination strategy to prepare a series of single-atomic Cu/ceria catalysts with varied oxygen vacancy concentrations for robust electrolytic reduction of CO2 to methane. The obtained Cu/ceria catalyst under H2 environment (Cu/ceria-H2) exhibits a methane Faraday efficiency (FECH4) of 70.03 % with a turnover frequency (TOFCH4) of 9946.7â h-1 at an industrial-scale current density of 150â mA cm-2 in a flow cell. Detailed studies indicate the copious oxygen vacancies in the Cu/ceria-H2 are conducive to regulating the surface microelectronic structure with stabilized Cu+ active center. Furthermore, density functional theory calculations and operando ATR-SEIRAS demonstrate that the Cu/ceria-H2 can markedly enhance the activation of CO2, facilitate the adsorption of pivotal intermediates *COOH and *CO, thus ultimately enabling the high selectivity for CH4 production. This study presents deep insights into designing effective electrocatalysts for CO2 to CH4 conversion by controlling the surface microstructure via the reaction atmosphere.
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Solution combustion (SC) remains among the most promising synthetic strategies for the production of crystalline nanopowders from an aqueous medium, due to its easiness, time and cost-effectiveness, scalability and eco-friendliness. In this work, this method was selected to obtain anisometric ceria-based nanoparticles applied as catalysts for the direct synthesis of dimethyl carbonate. The catalytic performances were studied for the ceria and Fe-doped ceria from SC (CeO2-SC, Ce0.9Fe0.1O2-SC) in comparison with the ceria nanorods (CeO2-HT, Ce0.9Fe0.1O2-HT) obtained by hydrothermal (HT) method, one of the most studied systems in the literature. Indeed, the ceria nanoparticles obtained by SC were found to be highly crystalline, platelet-shaped, arranged in a mosaic-like assembly and with smaller crystallite size (≈6â nm vs. ≈17â nm) and higher surface area (80â m2 g-1 vs. 26â m2 g-1) for the undoped sample with respect to the Fe-doped counterpart. Although all samples exhibit an anisometric morphology that should favor the exposition of specific crystalline planes, HT-samples showed better performances due to higher oxygen vacancies concentration and lower amount of strong basic and acid sites.
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The considerable challenge of wound healing remains. In this study, we fabricated a novel multifunctional core-shell nanofibrous scaffold named EGF@BSP-CeO2/PLGA (EBCP), which is composed of Bletilla striata polysaccharide (BSP), Ceria nanozyme (CeO2) and epidermal growth factor (EGF) as the core and poly(lactic-co-glycolic acid) (PLGA) as the shell via an emulsion electrospinning technique. An increase in the BSP content within the scaffolds corresponded to improved wound healing performance. These scaffolds exhibited increased hydrophilicity and porosity and improved mechanical properties and anti-UV properties. EBCP exhibited sustained release, and the degradation rate was <4 % in PBS for 30 days. The superior biocompatibility was confirmed by the MTT assay, hemolysis, and H&E staining. In addition, the in vitro results revealed that, compared with the other groups, the EBCP group presented excellent antioxidant and antibacterial effects. More importantly, the in vivo results indicated that the wound closure rate of the EBCP group reached 94.0 % on day 10 in the presence of H2O2. The results demonstrated that EBCP could comprehensively regulate the wound microenvironment, possess hemostatic abilities, and significantly promote wound healing. In conclusion, the EBCP is promising for facilitating the treatment of infected wounds and represents a potential material for clinical applications.
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Nanofibras , Orchidaceae , Polisacáridos , Andamios del Tejido , Cicatrización de Heridas , Cicatrización de Heridas/efectos de los fármacos , Nanofibras/química , Polisacáridos/química , Polisacáridos/farmacología , Animales , Andamios del Tejido/química , Orchidaceae/química , Cerio/química , Cerio/farmacología , Ratones , Copolímero de Ácido Poliláctico-Ácido Poliglicólico/química , Antibacterianos/farmacología , Antibacterianos/química , Antioxidantes/farmacología , Antioxidantes/química , Factor de Crecimiento Epidérmico/farmacología , Ratas , Materiales Biocompatibles/química , Materiales Biocompatibles/farmacología , Masculino , Porosidad , HumanosRESUMEN
Fe-modified Cu catalysts with CeO2 support, prepared by the impregnation method, were subjected to physicochemical analysis and catalytic tests in the steam reforming of methanol (SRM). Physicochemical studies of the catalysts were carried out using the XRF, TEM, STEM-EDS, XRD, TPR and nitrogen adsorption/desorption methods. XRD, TEM studies and catalytic tests of the catalysts were carried out at two reduction temperatures, 260 °C and 400 °C, to determine the relationship between the form and oxidation state of the active phase of the catalysts and the catalytic properties of these systems in the SRM. Additionally, the catalysts after the reaction were analysed for the changes in the structure and morphology using TEM methods. The presented results show that the composition of the catalysts, morphology, structure, form and oxidation state of the Cu and Fe active metals in the catalysts and the reaction temperature significantly impact their activity, selectivity and stability in the SRM process. The gradual deactivation of the studied catalysts under SRM conditions could result from the forming of carbon deposits and/or the gradual oxidation of the copper and iron phases under the reaction conditions.
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Modification of CeO2 (ceria) with 3d transition metals, particularly iron, has been proven to significantly enhance its catalytic efficiency in oxidation or combustion reactions. Although this phenomenon is widely reported, the nature of the iron-ceria interaction responsible for this improvement remains debated. To address this issue, we prepared well-defined model FeOx/CeO2(111) catalytic systems and studied their structure and interfacial electronic properties using photoelectron spectroscopy, scanning tunneling microscopy, and low-energy electron diffraction, coupled with density functional theory (DFT) calculations. Our results show that under ultrahigh vacuum conditions, Fe deposition leads to the formation of small FeOx clusters on the ceria surface. Subsequent annealing results in the growth of large amorphous FeOx particles and a 2D FeOx layer. Annealing in an oxygen-rich atmosphere further oxidizes iron up to the Fe3+ state and improves the crystallinity of both the 2D layer and the 3D particles. Our DFT calculations indicate that the 2D FeOx layer interacts strongly with the ceria surface, exhibiting structural corrugations and transferred electrons between Fe2+/Fe3+ and Ce4+/Ce3+ redox pairs. The novel 2D FeOx/CeO2(111) phase may explain the enhancement of the catalytic properties of CeO2 by iron. Moreover, the corrugated 2D FeOx layer can serve as a template for the ordered nucleation of other catalytically active metals, in which the redox properties of the 2D FeOx/CeO2(111) system are exploited to modulate the charge of the supported metals.
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In this study, we utilized various Pr-doped CeO2 catalysts (Pr=5, 10, 20, and 30â wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water-gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure-activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr-CeO2 catalysts at optimum Pr loading (10â wt.%) exhibit a superior CO conversion (88 %) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.
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Atomic-scale insights into the interactions between metals and supports play a crucial role in optimizing catalyst design, understanding catalytic mechanisms, and enhancing chemical conversion processes. The effects of oxide support on the dynamic behavior of supported metal species during pretreatments or reactions have been attracting a lot of attention; however, very less systematic integrations are carried out experimentally using real catalysts. In this study, we here utilized facet-controlled CeO2 as examples to explore their influence on the supported Pt species (1.0 wt %) during the reducing and oxidizing pretreatments that are typically applied in heterogeneous catalysts. By employing a combination of microscopy, spectroscopy, and first-principles calculations, it is demonstrated that the exposed crystal facets of CeO2 govern the evolution behavior of supported Pt species under different environmental conditions. This leads to distinct local coordinations and charge states of the Pt species, which directly influence the catalytic reactivity and can be leveraged to control the catalytic performance for CO oxidation reactions.