Modularization of Regional Electronic Structure over Defect-Rich CeO2 Rods for Enhancing Photogenerated Charge Transfer and CO2 Activation.

Oxygen vacancy (OV) engineering has been widely applied in different types of metal oxide-based photocatalytic reactions. Our study has shown that the redistributed OVs resulting from voids in CeO2 rods lead to significant differences in the band structure in space. The flat energy band within the highly crystallized bulk region hinders the recombination of photogenerated carrier pairs during the transfer process. The downward curved energy band in the surface region enhances the activation of the absorbents. Therefore, the localization of the band structure through crystal structure regionalization renders V-CeO2 capable of achieving efficient utilization of photogenerated carriers. Practically, the V-CeO2 rod shows a remarkable turnover number of 190.58 µmol g-1 h-1 in CO2 photoreduction, which is ∼9.4 times higher than that of D-CeO2 (20.46 µmol g-1 h-1). The designed modularization structure in our work is expected to provide important inspiration and guidance in coordinating the kinetic behavior of carriers in OV defect-rich photocatalysts.

Pt Single Atoms Supported on Defect Ceria as an Active and Stable Dual-Site Catalyst for Alkaline Hydrogen Evolution.

This work evaluates the feasibility of alkaline hydrogen evolution reaction (HER) using Pt single-atoms (1.0 wt %) on defect-rich ceria (Pt1/CeOx) as an active and stable dual-site catalyst. The catalyst displayed a low overpotential and a small Tafel slope in an alkaline medium. Moreover, Pt1/CeOx presented a high mass activity and excellent durability, competing with those of the commercial Pt/C (20 wt %). In this picture, the defective CeOx is active for water adsorption and dissociation to create H* intermediates, providing the first site where the reaction occurs. The H* intermediate species then migrate to adsorb and react on the Pt2+ isolated atoms, the site where H2 is formed and released. DFT calculations were also performed to obtain mechanistic insight on the Pt1/CeOx catalyst for the HER. The results indicate a new possibility to improve the state-of-the-art alkaline HER catalysts via a combined effect of the O vacancies on the ceria support and Pt2+ single atoms.

Active-learning for global optimization of Ni-Ceria nanoparticles: The case of Ce4-xNixO8- x (x = 1, 2, 3).

Ni-CeO2 nanoparticles (NPs) are promising nanocatalysts for water splitting and water gas shift reactions due to the ability of ceria to temporarily donate oxygen to the catalytic reaction and accept oxygen after the reaction is completed. Therefore, elucidating how different properties of the Ni-Ceria NPs relate to the activity and selectivity of the catalytic reaction, is of crucial importance for the development of novel catalysts. In this work the active learning (AL) method based on machine learning regression and its uncertainty is used for the global optimization of Ce(4-x)NixO(8-x) (x = 1, 2, 3) nanoparticles, employing density functional theory calculations. Additionally, further investigation of the NPs by mass-scaled parallel-tempering Born-Oppenheimer molecular dynamics resulted in the same putative global minimum structures found by AL, demonstrating the robustness of our AL search to learn from small datasets and assist in the global optimization of complex electronic structure systems.

Theoretical study of structure sensitivity on ceria-supported single platinum atoms and its influence on carbon monoxide adsorption.

Density functional theory (DFT) calculations explore the stability of a single platinum atom on various flat, stepped, and defective ceria surfaces, in the context of single-atom catalysts (SACs) for the water-gas shift (WGS) reaction. The adsorption properties and diffusion kinetics of the metal strongly depend on the support termination with large stability on metastable and stepped CeO2(100) and (210) surfaces where the diffusion of the platinum atom is hindered. At the opposite, the more stable CeO2(111) and (110) terminations weakly bind the platinum atom and can promote the growth of metallic clusters thanks to fast diffusion kinetics. The adsorption of carbon monoxide on the single platinum atom supported on the various ceria terminations is also sensitive to the surface structure. Carbon monoxide weakly binds to the single platinum atom supported on reduced CeO2(111) and (211) terminations. The desorption of the CO2 formed during the WGS reaction is thus facilitated on the latter terminations. A vibrational analysis underlines the significant changes in the calculated scaled anharmonic CO stretching frequency on these catalysts.

Boosting Electrochemical Nitrogen Fixation via Regulating Surface Electronic Structure by CeO2 Hybridization.

Electrocatalytic nitrogen reduction reaction (NRR) paves a sustainable way to produce NH3 but suffering from the relatively low NH3 yield and poor selectivity. High-performance NRR catalysts and a deep insight into the structure-performance relationship are higher desired. Herein, a molten-salt approach is developed to synthesize tiny CeO2 nanoparticles anchored by ultra-thin MoN nanosheets as advanced catalysts for NRR. Specifically, a considerably high NH3 yield rate of 27.5 µg h-1 mg-1 with 17.2% Faradaic efficiency (FE) can be achieved at -0.3 V vs (RHE) under ambient conditions. Experimental and density functional theory (DFT) calculations further point out that the incorporation of MoN with CeO2 can promotes the enlargement of the electron deficient area of nitrogen vacancy site. The enlarged electron deficient area contributes to the accommodation of lone pair electrons of N2, which dramatically improves the N2 adsorption/activation and the key intermediates (*NNH and *NH3) generation, thus boosting the NRR performance.

Hetero-Interface Engineering on 9.0 wt% CoOx -Doped CeO2 Nanorods as Electromagnetic Wave Absorber and Integrated into Multifunctional Aerogel.

Ceria (CeO2 ) becomes a promising candidate as electromagnetic wave absorbing materials (EWAMs) for their abundant natural source, rich oxygen vacancy, charge conversion, and electron transfer abilities. However, it remains challenging to regulate its nanoscale and atom-scale composition to optimize the absorbing performance and develop high-performance commercial devices. Herein, a facile method to large-scale synthesis CeO2 @Co-x% (x = 5, 7, 9, 11, 13) series EWAMs with diverse amounts of decorated CoOx is presented. By modulating the ratio of doped CoOx , a rational hetero-interface is created in CeO2 @Co-9% to enhance natural and exchange resonances, improving magnetic loss capability and optimizing impedance matching. Doped CoOx promotes the charge accumulation, interfacial polarization, and multiple scattering of the CeO2 for strengthening the EW absorption and attenuation, which display superb minimum reflective loss (RLmin ) of -74.4 dB with a wide effective absorbing bandwidth (EAB) of 5.26 GHz. Furthermore, a dual crosslinking strategy is employed to fabricate CeO2 @Co-9% into an aerogel device with integrated lightweight, heat insulation, compression resistance, and fame-retardant functions. This work presents an excellent example of large-scale fast synthesis of high-performance CeO2 -based EWAMs and multiplication 3D devices.

Bacterial Susceptibility to Ceria Nanoparticles: The Critical Role of Surrounding Molecules.

Investigating the ternary relationship among nanoparticles (NPs), their immediate molecular environment, and test organisms rather than the direct interaction between pristine NPs and test organisms has been thrust into the mainstream of nanotoxicological research. Diverging from previous work that predominantly centered on surrounding molecules affecting the toxicity of NPs by modulating their nanoproperties, this study has unveiled a novel dimension: surrounding molecules altering bacterial susceptibility to NPs, consequently impacting the outcomes of nanobio interaction. The study found that adding nitrate as the surrounding molecules could alter bacterial respiratory pathways, resulting in an enhanced reduction of ceria NPs (nanoceria) on the bacterial surfaces. This, in turn, increased the ion-specific toxicity originating from the release of Ce3+ ions at the nanobio interface. Further transcriptome analysis revealed more mechanistic details underlying the nitrate-induced changes in the bacterial energy metabolism and subsequent toxicity patterns. These findings offer a new perspective for the deconstruction of nanobio interactions and contribute to a more comprehensive understanding of NPs' environmental fate and ecotoxicity.

Hydroxyls on CeO2 Support Promoting CuO/CeO2 Catalyst for Efficient CO Oxidation and NO Reduction by CO.

Transition metal catalysts, such as copper oxide, are more attractive alternatives to noble metal catalysts for emission control due to their higher abundance, lower cost, and excellent catalytic activity. In this study, we report the preparation and application of a novel CuO/CeO2 catalyst using a hydroxyl-rich Ce(OH)x support for CO oxidation and NO reduction by CO. Compared to the catalyst prepared from a regular CeO2 support, the new CuO/CeO2 catalyst prepared from the OH-rich Ce(OH)x (CuO/CeO2-OH) showed significantly higher catalytic activity under different testing conditions. The effect of OH species in the CeO2 support on the catalytic performance and physicochemical properties of the CuO/CeO2 catalyst was characterized in detail. It is demonstrated that the abundant OH species enhanced the CuOx dispersion on CeO2, increased the CuOx-CeO2 interfaces and surface defects, promoted the oxygen activation and mobility, and boosted the NO adsorption and dissociation on CuO/CeO2-OH, thus contributing to its superior catalytic activity for both CO oxidation and NO reduction by CO. These results suggest that the OH-rich Ce(OH)x is a superior support for the preparation of highly efficient metal catalysts for different applications.

Polymer-enhanced peroxidase activity of ceria nanozyme for highly sensitive detection of alkaline phosphatase.

Nanoceria have demonstrated a wide array of catalytic activity similar to natural enzymes, holding considerable significance in the colorimetric detection of alkaline phosphatase (ALP), which is a biomarker of various biological disorders. However, the issues of physiological stability and formation of protein corona, which are strongly related to their surface chemistry, limit their practical application. In this work, CeO2 nanoparticles characterized by enhanced dimensional uniformity and specific surface area were synthesized, followed by encapsulation with various polymers to further increase catalytic activity and physiological stability. Notably, the CeO2 nanoparticles encapsulated within each polymer exhibited improved catalytic characteristics, with PAA-capped CeO2 exhibiting the highest performance. We further demonstrated that the PAA-CeO2 obtained with enhanced catalytic activity was attributed to an increase in surface negative charge. PAA-CeO2 enabled the quantitative assessment of AA activity within a wide concentration range of 10 to 60 µM, with a detection limit of 0.111 µM. Similarly, it allowed for the evaluation of alkaline phosphatase activity throughout a broad range of 10 to 80 U/L, with a detection limit of 0.12 U/L. These detection limits provided adequate sensitivity for the practical detection of ALP in human serum.

Fluorimetric determination of tetracycline antibiotics in animal derived foods using boron and nitrogen co-doped ceria-based nanoparticles.

An innovative synthesis of boron and nitrogen co-doped ceria-based nanoparticles (B/N-CeFNPs) with bright blue fluorescence emission is reported using the hydrothermal method. Based on the aggregation-induced emission enhancement (AIEE) effect between B/N-CeFNPs and chlortetracycline (CTC), a rapid detection method for CTC through fluorescence enhancement was developed. In addition, through the electron transfer process (ET), fluorescence resonance energy transfer (FRET) effect and static quenching between B/N-CeFNPs and oxytetracycline (OTC), a ratio fluorescence strategy for detecting OTC was generated. The fluorescence of B/N-CeFNPs at 410 nm can be effectively quenched by OTC, and new fluorescence emission appears at a wavelength of 500 nm. B/N-CeFNPs showed good linear responses with CTC and OTC in the range 0.1-1 µM and 1-40 µM, respectively. This system was used to simultaneously detect the CTC and OTC in milk and honey, realizing multi-residues detection of TCs in actual samples by using the same ceria-based fluorescence nanomaterial.

Microwave-Based State Diagnosis of Three-Way Catalysts: Impact Factors and Application Recommendations.

This study reassesses an overview of the potential of the radio frequency (RF)-based state diagnostics of three-way catalysts (TWC) based on a previous study with an emphasis on the defect chemistry of the catalyst material during reoxidation and reduction. Some data are based on the previous works but are newly processed, and the signal parameters resonant frequency and inverse quality factor are evaluated with respect to applicability. The RF-based method uses electromagnetic resonances in a cavity resonator to provide information on the storage level of the oxygen storage component. The analysis focuses on a holistic investigation and evaluation of the major effects influencing the RF signal during operation. On the one hand, the response to the oxygen storage behavior and the resolution of the measurement method are considered. Therefore, this study merges original data from multiple former publications to provide a comprehensive insight into important measurement effects and their defect chemistry background. On the other hand, the most important cross-sensitivities are discussed and their impact during operation is evaluated. Additionally, the effect of catalyst aging is analyzed. The effects are presented separately for the two resonant parameters: resonant frequency and (unloaded) quality factor. Overall, the data suggest that the quality factor has a way higher signal quality at low temperatures (<400 °C) and the resonant frequency is primarily suitable for high operating temperatures. At most operating points, the quality factor is even more robust against interferences such as exhaust gas stoichiometry and water content. Correctly estimating the catalyst temperature is the most important factor for reliable results, which can be achieved by combining the information of both resonant signals. In the end, the data indicate that microwave-based state diagnosis is a powerful system for evaluating the oxygen storage level over the entire operating range of a TWC. As a research tool and in its application, the system can therefore contribute to the improvement of the emission control of future gasoline vehicles.

Hydrogenolysis of Glycerol over NiCeZr Catalyst Modified with Mg, Cu, and Sn at the Surface Level.

Biomass valorization is an essential strategy for converting organic resources into valuable energy and chemicals, contributing to the circular economy, and reducing carbon footprints. Glycerol, a byproduct of biodiesel production, can be used as a feedstock for a variety of high-value products and can contribute to reducing the carbon footprint. This study examines the impact of surface-level modifications of Mg, Cu, and Sn on Ni-Ce-Zr catalysts for the hydrogenolysis of glycerol, with in situ generated hydrogen. The aim of this approach is to enhance the efficiency and sustainability of the biomass valorization process. However, the surface modification resulted in a decrease in the global conversion of glycerol due to the reduced availability of metal sites. The study found that valuable products, such as H2 and CH4 in the gas phase, and 1,2-PG in the liquid phase, were obtained. The majority of the liquid fraction was observed, particularly for Cu- and Sn-doped catalysts, which was attributed to their increased acidity. The primary selectivity was towards the cleavage of the C-O bond. Post-reaction characterizations revealed that the primary causes of deactivation was leaching, which was reduced by the inclusion of Cu and Sn. These findings demonstrate the potential of Cu- and Sn-modified Ni-Ce-Zr catalysts to provide a sustainable pathway for converting glycerol into value-added chemicals.

PdPtVOx/CeO2-ZrO2: Highly efficient catalysts with good sulfur dioxide-poisoning reversibility for the oxidative removal of ethylbenzene.

The PdPtVOx/CeO2-ZrO2 (PdPtVOx/CZO) catalysts were obtained by using different approaches, and their physical and chemical properties were determined by various techniques. Catalytic activities of these materials in the presence of H2O or SO2 were evaluated for the oxidation of ethylbenzene (EB). The PdPtVOx/CZO sample exhibited high catalytic activity, good hydrothermal stability, and reversible sulfur dioxide-poisoning performance, over which the specific reaction rate at 160°C, turnover frequency at 160°C (TOFPd or Pt), and apparent activation energy were 72.6 mmol/(gPt⋅sec) or 124.2 mmol/(gPd⋅sec), 14.2 sec-1 (TOFPt) or 13.1 sec-1 (TOFPd), and 58 kJ/mol, respectively. The large EB adsorption capacity, good reducibility, and strong acidity contributed to the good catalytic performance of PdPtVOx/CZO. Catalytic activity of PdPtVOx/CZO decreased when 50 ppm SO2 or (1.0 vol.% H2O + 50 ppm SO2) was added to the feedstock, but was gradually restored to its initial level after the SO2 was cut off. The good reversible sulfur dioxide-resistant performance of PdPtVOx/CZO was associated with the facts: (i) the introduction of SO2 leads to an increase in surface acidity; (ii) V can adsorb and activate SO2, thus accelerating formation of the SOx2- (x = 3 or 4) species at the V and CZO sites, weakening the adsorption of sulfur species at the PdPt active sites, and hence protecting the PdPt active sites to be not poisoned by SO2. EB oxidation over PdPtVOx/CZO might take place via the route of EB â†’ styrene â†’ phenyl methyl ketone â†’ benzaldehyde â†’ benzoic acid â†’ maleic anhydride â†’ CO2 and H2O.

Synergy of Oxygen Vacancies and Base Sites for Transfer Hydrogenation of Nitroarenes on Ceria Nanorods.

CeO2 nanorod based catalysts for the base-free synthesis of azoxy-aromatics via transfer hydrogenation of nitroarenes with ethanol as hydrogen donor have been synthesized and investigated. The oxygen vacancies (Ov ) and base sites are critical for their excellent catalytic properties. The Ov , i.e., undercoordinated Ce cations, serve as the sites to activate ethanol and nitroarenes by lowering the energy barrier to transfer hydrogen from α-Csp3 -H in ethanol to the nitro group coupling it to the redox reactions between Ce3+ and Ce4+ . At the same time, the base sites catalyze the condensation step to selectively produce azoxy-aromatics. The catalytic route opens a much improved way to use non-noble metal oxides without additives for the selective functional group reduction and coupling reactions.

Highly Active Oxidation Catalysts through Confining Pd Clusters on CeO2 Nano-Islands.

CeO2-supported noble metal clusters are attractive catalytic materials for several applications. However, their atomic dispersion under oxidizing reaction conditions often leads to catalyst deactivation. In this study, the noble metal cluster formation threshold is rationally adjusted by using a mixed CeO2-Al2O3 support. The preferential location of Pd on CeO2 islands leads to a high local surface noble metal concentration and promotes the in situ formation of small Pd clusters at a rather low noble metal loading (0.5 wt %), which are shown to be the active species for CO conversion at low temperatures. As elucidated by complementary in situ/operando techniques, the spatial separation of CeO2 islands on Al2O3 confines the mobility of Pd, preventing the full redispersion or the formation of larger noble metal particles and maintaining a high CO oxidation activity at low temperatures. In a broader perspective, this approach to more efficiently use the noble metal can be transferred to further systems and reactions in heterogeneous catalysis.

Identifying the Structure of Supported Metal Catalysts Using Vibrational Fingerprints from Ab Initio Nanoscale Models.

Identifying active sites of supported noble metal nanocatalysts remains challenging, since their size and shape undergo changes depending on the support, temperature, and gas mixture composition. Herein, the anharmonic infrared spectrum of adsorbed CO is simulated using density functional theory (DFT) to gain insight into the nature of Pd nanoparticles (NPs) supported on ceria. The authors systematically determine how the simulated infrared spectra are affected by CO coverage, NP size (0.5-1.5 nm), NP morphology (octahedral, icosahedral), and metal-support contact angle, by exploring a diversity of realistic models inspired by ab initio molecular dynamics. The simulated spectra are then used as a spectroscopic fingerprint to characterize nanoparticles in a real catalyst, by comparison with in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments. Truncated octahedral NPs with an acute Pd-ceria angle reproduce most of the measurements. In particular, the authors isolate features characteristic of CO adsorbed at the metal-support interface appearing at low frequencies, both seen in simulation and experiment. This work illustrates the strong need for realistic models to provide a robust description of the active sites, especially at the interface of supported metal nanocatalysts, which can be highly dynamic and evolve considerably during reaction.

Regulation of the Oxidase Mimetic Activity of Ceria Nanoparticles by Buffer Composition.

Ceria nanoparticles (CNPs) are important typical nanozymes with multiple enzyme mimetic activities, which could facilitate the oxidation of organic dyes in acidic conditions, because of the oxidase mimetic activity. Usually, the regulation of oxidase mimetic activity is focused on the adjustment of the structure, morphology, composition, surface, and other factors of nanozymes. However, the influence of the surrounding environment is not considered, which is very important during the reaction process. In this work, the oxidase mimetic activity of CNPs in buffer solutions including citric acid, acetic acid and glycine buffer solutions was investigated, with the results that carboxyl group in buffer solution could adsorb the CNPs on the surface to promote the oxidase mimetic activity. Due to the chelation with the cerium ion, the enhancement is more significant by molecules with polycarboxylic groups, and the enhancement is more efficient by carboxyl molecules in buffer solution, compared with the modification of the carboxyl groups on the surface, because of easier operation and smaller steric hindrance. From the viewpoint of increasing the oxidase mimetic activity of CNPs, the work is expected to provide references for the selection of the reaction systems to optimize the oxidase mimetic activity in bio-detection applications.

Mechanism of NH3-SCR over P/CeO2 Catalysts Investigated by Operando Spectroscopies.

This study reports a comprehensive investigation into the active sites and reaction mechanism for the selective catalytic reduction of NO by NH3 (NH3-SCR) over phosphate-loaded ceria (P/CeO2). Catalyst characterization and density functional theory calculations reveal that H3PO4 and H2P2O6 species are the dominant phosphate species on the P/CeO2 catalysts under the experimental conditions. The reduction/oxidation half-cycles (RHC/OHC) were investigated using in situ X-ray absorption near-edge structure for Ce L3-edge, ultraviolet-visible, and infrared (IR) spectroscopies together with online analysis of outlet products (operando spectroscopy). The Ce4+(OH-) species, possibly adjacent to the phosphate species, are reduced by NO + NH3 to produce N2, H2O, and Ce3+ species (RHC). The Ce3+ species is reoxidized by aqueous O2 (OHC). The results from IR spectroscopy suggest that the RHC initiates with the reaction between NO and Ce4+(OH-) to yield Ce3+ and gaseous HONO, which then react with NH3 to produce N2 and H2O via NH4NO2 intermediates.

Visible light active hybrid silver decorated g-C3N4-CeO2 nanocomposite for ultrafast photocatalytic activity and toxicity evaluation.

Development of hybrid graphitic carbon nitride (GCN) nanocomposite is an emerging research area in wastewater treatment. Herein, hybrid visible light active photocatalyst of silver decorated polymeric graphitic carbon nitride and (Ag-GCN) with cerium oxide (CeO2) nanocomposite was prepared and characterized in detail. The Ag-GCN/CeO2 photocatalyst has successfully prepared by an electrostatic self-assembly approach. The synthesized Ag-GCN/CeO2 NCs photocatalysts are characterized by various physio-chemical techniques. Using the Ag-GCN/CeO2 catalyst, the excellent photodegradation efficiency of Acid yellow-36 (AY-36) and Direct yellow-12 (DY-12) dye solution were achieved 100% within 150 min sun light irradiation. The Ag-GCN/CeO2 rate constant values of 0.048 and 0.046/min has been determined for AY-36 and DR-12 dyes, respectively. The extraordinary photocatalytic activity is due to incorporation of CeO2 with Ag-GCN which play a significant role in visible light absorption, superior reactive oxygen generation (ROS) and excellent pollutant catalyst interaction. The toxicity of the photocatalytically degraded AY-36 and DR-12 dyes were measured using the soil nematode Caenorhabditis elegans, a well-established in vivo model in biology, by analyzing survival, physiological functions, intracellular ROS levels, and stress-protective gene expressions.

Engineering antioxidant ceria-zirconia nanomedicines for alleviating podocyte injury in rats with adriamycin-induced nephrotic syndrome.

BACKGROUND: Primary nephrotic syndrome (PNS) is characterized by edema, heavy proteinuria, hypoalbuminemia and hyperlipidemia. Moreover, podocyte injury is the key pathological change of PNS. Even though the pathophysiological etiology of PNS has not been fully understood, the production of excessive reactive oxygen species (ROS) plays an important role in the development and progression of the disease. Glucocorticoids are the first-line medications for patients with PNS, but their clinical use is hampered by dose-dependent side effects. Herein, we accelerated the rate of conversion from Ce4+ to Ce3+ by doping Zr4+ in ceria-zirconia nanomedicines to treat the PNS rat model by removal of ROS. RESULTS: The engineered Ce0.7Zr0.3O2 (7CZ) nanomedicines significantly improved the ROS scavenging ability of podocytes at a very low dose, enabling effective inhibition of podocyte apoptosis and actin cytoskeleton depolymerization induced by adriamycin (ADR). Accordingly, podocyte injury was effectively alleviated in rat models of ADR-induced nephrotic syndrome, as confirmed by serum tests and renal tissue staining. Moreover, the mRNA sequencing assay revealed the protective molecular signaling pathways of 7CZ nanomedicines in podocytes. CONCLUSION: 7CZ nanomedicines were highly effective in protecting against ADR-induced podocyte injury in vitro and in vivo at a very low concentration.