CeO2 Surface Research Articles

Role of Metal-Oxide Interfaces in Methanol Decomposition: Reaction of Methanol on CeO2/Ag(111) Inverse Model Catalysts.

Metal-oxide interfaces play a critical role in catalytic processes, such as methanol adsorption and decomposition reactions. In this work, we investigated methanol reactions on the inverse model CeO2/Ag(111) catalyst surfaces, i.e., submonolayer CeO2 films on Ag(111), under ultrahigh vacuum (UHV) conditions to specially address the role of CeO2-Ag interface in the catalytic methanol decomposition reactions. Using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and synchrotron radiation photoemission spectroscopy (SRPES), we found that, at the submonolayer ceria coverages, the CeO2 nanoislands exhibit a hexagonal CeO2(111) lattice with fully oxidized Ce4+ on Ag(111). At higher ceria coverages, multilayer ceria nanoislands form on the Ag(111) surface instead of a well-ordered film. A combination of temperature-programmed desorption (TPD) and SRPES reveals that methanol adsorbs dissociatively on the CeO2/Ag(111) surfaces at 110 K, resulting in the formation of methoxy groups. These methoxy groups subsequently decompose via two pathways: (i) interaction with lattice oxygen to produce formate species at 230 K, which then decompose to CO, and (ii) direct dehydrogenation of methoxy to formaldehyde. Notably, the surface with submonolayer CeO2 film on Ag(111) demonstrates low-temperature reactivity (440 K) for methoxy dehydrogenation to formaldehyde, which occurs at a much lower temperature, compared to the surface of multilayer CeO2 on Ag(111) surface (530 K). This finding emphasizes that the CeO2-Ag(111) interfaces provide unique active sites for methoxy dehydrogenation reactions.

Initial Stages of Water Absorption on CeO2 Surfaces at Very Low Temperatures for Understanding Anti-Icing Coatings

Abstract Anti-icing coatings are intended to prevent ice formation on surfaces, minimising the risk of surface-related damage and also reducing ice-related hazards in society. We demonstrate the usefulness of X-ray photoelectron spectroscopy (XPS) as a tool for investigating the anti-icing properties of surfaces simultaneously with their chemical composition by looking at the initial stages of water absorption on the surface of CeO2 coatings. CeO2 coatings are robust, hydrophobic, and transmit light, thus they are suitable for a range of applications. In this work, CeO2 coatings were grown by sputter deposition and transferred to an ultra-high vacuum chamber where they were cooled to ≈100 K and exposed to a H2O atmosphere at 1×10-8 mbar. XPS measurements were performed before and after the exposure to H2O, in-situ and at cryogenic temperatures. The chemical composition of CeO2 did not change significantly during the experiment. Additionally, XPS revealed that little to no ice formed on the surface of CeO2 after the H2O exposure at ≈100 K. In contrast, ice was observed all over the sample holder on which the CeO2 was mounted. These findings suggest CeO2 is a promising candidate for future anti-icing coatings and that XPS is a useful technique to investigate the anti-icing properties of surfaces.

Stabilizing Ni catalysts in biogas reforming via in situ carbon deposit removal by CeO2 oxygen vacancies.

Ni-based catalysts face significant challenges of carbon deposition during biogas reforming to syngas. Herein, we propose leveraging the in situ consumption of carbon deposits generated during biogas reforming through oxygen vacancies (Ov) on the surface of CeO2, ensuring enhanced activity and stability of the Ni3Fe/CeO2-rod structure catalyst. The catalyst exhibits an initial CH4 conversion of 80.4% and a CO2 conversion of 97.2%, with a mere 3.9% decline in CO2 conversion after 720 min.

Elucidating the intrinsic relationship between redox properties of CeO2 and CH4 oxidation activity: A theoretical perspective.

Methane (CH4) oxidation is an important reaction to reduce the greenhouse effect caused by incomplete combustion of CH4. Here, we explored the mechanism of CH4 oxidation catalyzed by CeO2 and Ni-doped CeO2, focusing on the redox properties of these catalyst surfaces, using density functional theory (DFT). We found that the barriers for CH4* activation and H2O* formation are correlated with the surface redox capacity, which is enhanced by Ni doping. Furthermore, the complete reaction mechanism is explored by DFT calculations and microkinetic simulations on bare and Ni-doped CeO2 surfaces. Our calculations suggest that the doping of Ni leads to a much higher overall reactivity, due to a balance between the CH4* activation and H2O* formation steps. These results provide insights into the CH4 oxidation mechanism and the intrinsic relationship between redox properties and the activity of CeO2 surfaces.

Selective catalytic reduction of NO with NH3 over HZSM-5/CeO2 hybrid catalysts: Relationship between acid structure and reaction mechanism

CeO2 is active in the NH3 selective catalytic reduction of NO (NH3-SCR) reaction due to its excellent redox properties. However, the low surface acidity of CeO2 limits its NH3-SCR activity. In this study, highly active HZSM-5-modified HZSM-5/CeO2 (Z/Ce) mixed oxide catalysts were prepared by a simple physical milling method. The HZSM-5 modification stimulated many thermally stable Brønsted-acid structures and high oxygen mobility on the surface of the Z/Ce catalysts, promoting the acid cycling pathways driven by redox macrocycles, and accelerating NO removal. The NO conversion of 25Z/Ce at 200–400 °C is about 34.8 %-62.3 % higher than that of CeO2. A series of physicochemical and in situ interfacial reactions were analyzed to explore the medium- and high-temperature reaction mechanism on the CeO2 surface. The Eley-Rideal reaction mechanism on the Lewis-acid structure with NO(g) as the reactant is deduced. When HZSM-5 modified CeO2, more NO was activated to NO2(g) on the surface of the Z/Ce catalyst at medium and high temperatures (300 °C). This significantly enhanced the Eley-Rideal reaction mechanism with NO2(g) as the main reactant on the Brønsted-acid structure as well as the occurrence of the “Fast-SCR” reaction. This work provides a simple method to improve the performance of CeO2 in the NH3-SCR reaction and elucidates the reaction mechanism.

Unexpected nanoscale CeO2 structural transformations induced by ecologically relevant phosphate species

In the present study, the dissolution and microstructural transformation of CeO2 nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO2 NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO4. Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO2 NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO2 surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh2(PO4)3, as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO2 NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO2 NPs.

Strong Metal–Support Interaction Induces Dual Reaction Sites for Ultrasensitive and Stable NO2 Detection in Extreme Environments

AbstractThe tripartite combination of a high density and stability of surface reaction sites, complemented by the longevity and efficient transfer of interface carriers, along with the effective adsorption and activation of target gas molecules, jointly determines the efficiency of chemiresistors. In this work, the strong metal–support interaction (SMSI) of Pt─Ce3+ is formed by the NaBH4 reduction method and thus prepares metal‐dynamically stable PtNR─CeO2 with Pt─Ce3+ and Pt─Pt reaction sites. The formation of SMSI induces the recombination of the chemical structure of the CeO2 surface causing the localization of electron‐rich Ce3+, which greatly increases the charge concentration at the interface. The experimental findings of the strong interaction of Pt─Ce3+ bonding and the catalytic effect of Pt optimized the adsorption mode of PtNR─CeO2 on target gas, which maintains stable catalytic activity at 20–500 °C and achieving a notable detection response value of 1.43 for 20 ppb NO2. This work offers fresh insights into designing stable oxide chemiresistors with efficiency and stability by customizing reaction sites at the atomic level.

Oxygen and Electron Storage Effects in W-Modified Ceria Catalysts for Ammonia Conversion.

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.

Constructing Ce–OH groups on CeO2 for enhancing removal and recovery of uranium from wastewater and seawater

Efficient recovery of uranium from wastewater and seawater provides an important guarantee for the sustainable growth of nuclear energy. Herein, we skillfully use the alkali etching method to construct CeO2 hollow spheres rich in Ce–OH groups for the removal and recovery of uranium from water matrixes. It is found that the CeO2 exhibits fast adsorption kinetics (equilibrium time within 10 min) and moderate adsorption capacity (143.1 mg/g), and the removal efficiency of low concentration uranium (0.1 g/L and 1 g/L) reaches 100% within 1 min of adsorption. Moreover, the adsorption of uranium by CeO2 is almost unaffected by common anions and cations in the environment, even if the concentration of anions is 1000 times that of uranium. More importantly, the CeO2 can enrich uranium concentration in seawater by 167.9 times and the recovery rate reaches 83.9%. Mechanistic studies reveal that the adsorption of uranium by CeO2 is mainly attributed to the rich Ce–OH groups on the surface of CeO2, resulting in the rapid adsorption of U(VI) and mainly forms a single-bridge model. The findings of this study provide a green and efficient path for the removal and recovery of uranium from wastewater and seawater.

Bulk, overlap and surface effects of swift heavy ions in CeO2

Formation of tracks of swift heavy ions decelerating in the electronic stopping regime in CeO2 was studied, combining the Monte Carlo code TREKIS with molecular dynamics. We show that strong lattice disordering (melting) followed by structure recovery form finally a damaged ion track consisting of a discontinuous crystalline region in CeO2. Normal ion impacts result in appearance of spherical crystalline hillocks on CeO2 surface. The solid-vacuum interface strongly suppresses the recrystallization of the near-surface layers, forming conically shaped tracks with several tens of nanometers lengths. Grazing ion irradiation induces intensive material expulsion from the surface forming finally grooves surrounded by nanohillocks. The processes of surface nanostructures formation is similar to those observed previously in CaF2 which has the similar crystalline structure, however requires much longer recrystallization time. Recent experimental data confirm the simulation results.

Polyoxometalates-Mediated Selectivity in Pt Single-Atoms on Ceria for Environmental Catalysis.

Optimizing the reactivity and selectivity of single-atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates-mediated electronic interaction (PMEI) in a Pt single-atom catalyst supported on CeO2 modified with Keggin-type phosphotungstate acid (HPW), labeled as Pt1/CeO2-HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on CeO2 surface. Electrons are transferred from ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron-deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2-HPW leads to improved degradation of NH3, N2 selectivity in the NO conversion, and CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis applications.

Transition-Metal-Doped CeO2 for the Reverse Water-Gas Shift Reaction: An Experimental and Theoretical Study on CO2 Adsorption and Surface Vacancy Effects.

Transition metal-doped ceria (M-CeO2) catalysts (M = Fe, Co, Ni and Cu) with multiple loadings were experimentally investigated for reverse water gas shift (RWGS) reaction. Density functional theory (DFT) calculations were performed to benchmark the properties that impact catalytic activity of CO2 reduction. Temperature-programmed desorption (TPD) was conducted to study the CO2 binding strength on doped CeO2 surfaces; the trend of the energy along increasing metal loading agrees with the DFT calculations. Notably, CO2 dissociative adsorption energy and oxygen vacancy (OV) formation energy are key descriptors obtained from both DFT and experiments, which can be used to evaluate catalytic performance. Results show the effectiveness of transition metal doping in enhancing CO2 adsorption and reducibility of the surfaces, with Fe showing particularly promising results, i.e., CO2 conversion higher than 56% at 600 °C and 100% selectivity to CO. Cu exhibits 100% selectivity to CO but low CO2 conversion, while Co and Ni showed notable ability of methanation, particularly at high loadings. This study finds that an effective CeO2 based RWGS catalyst corresponds to OV sites that have low OV formation energies for surface reduction, and moderate CO2 adsorption energies for strong interaction with the surface to promote C-O bond scission.

Investigation into geometric configurations and electronic properties of CeO2-supported gold clusters

A detailed understanding of the geometric structure and electronic properties of gold nanoparticles on the ceria surface is crucial for comprehending their unique catalytic activity. Using the first-principles method based on density functional theory, the adsorption of Aux (x = 1–4) clusters on the CeO2(111) surface was studied. It was discovered that the standing configurations of Au2 and Au3, as well as the tetrahedral structure of Au4, are the most stable adsorption structures. The stability of these configurations is jointly determined by the number and strength of Au-Au bonds, the Au-O bonding energy, and the interaction dynamics between the clusters and the substrate. The analysis of Bader charge, difference charge density and density of states suggested that lattice relaxation and electronic localization occur in the reduced Ce3+. The reduced amount and location of Ce3+ are significantly influenced by the position and charge transfer amount of Aux cluster. The adsorption of CO on Au4/CeO2(111) indicated that stronger Au-C bonding energy due to the hybridization of Au-5d and C-2p, thereby enhancing the catalytic activity for CO oxidation reactions.

Enhanced chemical mechanical polishing (CMP) performance of porous self-assembled spherical cerium oxide via RE(La/Pr/Nd) doping

With the linewidth of integrated circuits has progressively narrowed, imposing higher demands on the chemical mechanical polishing (CMP) process. Cerium oxide nanoparticles are widely used as abrasives in CMP, with their physical structure and the surface content of Ce3+ ions and oxygen vacancies directly affecting their CMP performance. Here in, we synthesized La/Pr/Nd doped CeO2 with the porous self-assembled spherical structures. Doping with La/Pr/Nd reduced the grain size of cerium oxide, increased its specific surface area, decreased the pore size, and increased the pore volume. HR-TEM analysis shows that the porous self-assembled spherical CeO2 primarily exposes the (111) crystal facet. Additionally, the density functional theory (DFT) calculation, XPS, H2-TPR and XANES analyses shown that doping of La/Pr/Nd facilitated the formation of oxygen vacancies and increased the Ce3+ content on the (111) crystal facet of the CeO2. La atoms are more likely to stabilize on the CeO2 (111) surface compared to Pr and Nd atoms. The CMP results indicated that, The La-CeO2 exhibited a higher MRR of 338 ± 7.54 nm/min, which is a 35 % increase compared to p-CeO2, and achieved superior surface roughness (Ra = 0.201 ± 0.010 nm).

DFT insights into oxygen vacancy formation and chemical looping dry reforming of methane on metal-substituted CeO2 (111) surface

DFT insights into oxygen vacancy formation and chemical looping dry reforming of methane on metal-substituted CeO2 (111) surface

A comparative DFT study on NO2 adsorption and sensing activities of pristine, reduced and Pr3+-doped CeO2 (110) surface

Surface site activation enhances the sensing properties of the CeO2 (110) surface. Herein, the adsorption of nitrogen dioxide (NO2) on pristine and modified CeO2 (110) surfaces has been studied in detail using quantum chemical calculation. The introduction of the single praseodymium atom on the CeO2 surface reduces its band gap from 1.93 to 0.53 eV, which in turn enhances the adsorption energy from -0.58 (pristine) to -1.34 eV (doped) and also prolongs the desorption time, indicating stronger adsorption ability. The density of states (DOS) and projected density of states (PDOS) analyses reveal that Pr doping modifies the electronic properties of the CeO2 (110) surface which improves NO2 sensitivity. Further, it is also observed that 0.57 eV increase in the work function for NO₂ adsorption on Pr doped CeO2 surface, indicating stronger interaction compared to the pristine CeO2. In contrast, reduced CeO2 surfaces do not exhibit any significant change in sensing properties. Thus, it is understood that Pr-doped CeO2 (Pr/CeO2) surfaces exhibit better stability and sensitivity towards NO2 adsorption compared to pristine and reduced surfaces. Therefore, this study provides insight into the rational design of advanced gas sensing materials based on modified CeO2 (110) surfaces, contributing to the development of an efficient air quality monitoring system.

Boosting CO oxidation performance via reaction-induced single-atom active site: DFT and microkinetic investigation of a unified CO oxidation mechanism on Gd-doped ceria supported copper catalysts

Single-atom (SA) catalysts have emerged as a pivotal area drawing extensive research interest due to their high catalytic activities. However, SA catalysts are often plagued by the aggregation and deactivation of SA sites under reaction conditions. This study focuses on CO oxidation over Gd-doped ceria supported Cu catalysts and aims to provide a new strategy to stabilize the SA site, in which a Cu SA site is “prestored” in a relatively stable Cu cluster and can be dynamically activated under reaction conditions. Three typical Cu10/CeO2 catalyst models were built with different Gd-doping contents, which are pristine Cu10/CeO2, Cu10/Gd0.125Ce0.875O2, and Cu10/Gd0.25Ce0.75O2, respectively. We performed density functional theory (DFT) calculations on the Cu10/Gd-CeO2 system to investigate the adsorption of CO and O2 molecules, the formation of surface oxygen vacancy (OV) and dynamic Cu SA site, and potential energy surfaces of CO oxidation process. Ab initio thermodynamic analysis suggests that the saturation adsorption of CO on Cu10 and high Gd-doping in CeO2 lead to a spontaneously formed single Cu−CO site and an OV defect on ceria surface. The CO oxidation process is identified as a two-paths-coupled catalytic cycle, in which Path I is activated by the terminal O atom of adsorbed O2 at surface OV site while Path II initiates with the lattice O atom of CeO2 surface. The microkinetic modeling demonstrates that the dominant pathway is Path I for the undoped and low-doping cases, and Path II for the high-doping case which exhibits a novel mechanism for CO oxidation and the highest reaction activity due to the participation of the dynamic SA site.

Sustainable catalytic hydrogenation of high concentration nitrate to ammonia over Ruthenium-based catalysts

Elevated nitrate levels in natural water bodies significantly disrupt the global nitrogen cycle and pose a substantial environmental and human health risk. This study investigates the selective conversion of nitrate to ammonia via catalytic hydrogenation. This highly efficient and selective process offers a sustainable alternative to traditional ammonia production methods while simultaneously addressing nitrate pollution. Ruthenium (Ru) catalysts supported on ceria (CeO2), titania (TiO2), and tin dioxide (SnO2) were synthesized using a simple impregnation method, incorporating oxygen vacancies and low Palladium (Pd) loadings (0.25–0.5 wt%) to enhance catalytic performance. Ru-Pd/CeO2 exhibited superior activity and selectivity, maintaining near 100 % ammonia selectivity across various nitrate concentrations. At 75 °C, complete conversion of 2000 ppm nitrate to ammonia was achieved within 80 min using Ru-Pd/CeO2, and the yield of ammonia can reach up to 16440 mg•h−1•gRu-1. Subsequent ammonia enrichment through evaporation yielded pure ammonia solutions up to 3.6 wt%. Characterization and theoretical calculations suggest that abundant oxygen vacancies on the CeO2 surface and efficient hydrogen spillover from Pd nanoparticles synergistically contribute to the Ru-Pd/CeO2 catalyst’s superior performance. The catalyst exhibited excellent stability and reusability, maintaining high activity and selectivity over four cycles. This research presents a promising strategy for addressing nitrate pollution in water bodies while offering a sustainable and environmentally friendly route for ammonia synthesis. The findings of this study lay the foundation for further advancing and potentially implementing catalytic hydrogenation technology for nitrate pollution remediation and ammonia synthesis.

Development of calcium phosphate cement composed of silica-modified hydroxyapatite, cerium oxide, and silica as an osteoporotic bone filler

Calcium phosphate cement (CPC), composed of silica-modified hydroxyapatite (HA-SiO2), cerium oxide (CeO2), and silica (SiO2), was developed as an osteoporosis bone filler. The effect of CeO2 and SiO2 content on the CPC's properties, such as crystal parameters, surface properties, antibacterial activity, and toxicity properties, were studied. HA-SiO2 was prepared using the sol-gel method, while CeO2 was prepared using the precipitation method. HA in HA-SiO2 has crystal properties similar to pure HA. Synthesized CeO2 contains Ce3+ and Ce4+ ions with Ce3+/Ce4+ = 0.34. Computational calculation predicted that the CeO2 (111) surface and glycine molecule interaction was categorized as chemisorption. Moreover, CeO2 has antibacterial activity toward Escherichia coli and Staphylococcus aureus. Combining HA-SiO2 and CeO2 did not change the adsorption-desorption isotherm curve type, but slightly decreased the surface area, total pore volume, and average pore. Increasing the percentage of CeO2 and adding 10 % SiO2 (w/w) affected the particle's size and CeO2 distribution. However, CPC lost antibacterial activity toward Staphylococcus aureus but adding 10 % SiO2 (w/w) increases the bacterial activity toward Escherichia coli close to that of pure CeO2. The MTT assay using pre-osteoblast MC3T3E1 cells showed that the CPC has IC50 = 4227 μg/ml or is nontoxic.

Atomic-level insights into CeO2 performance: Chemical interactions in CMP explored through CeO2-SiO2 studies

This study explores the effects of atomic-level factors on the performance of CeO2 when interacting with SiO2 films. It specifically examines how different precursors, the ratio of Ce to OH, and reaction temperatures influence outcomes. Our findings reveal that smaller particles, around 5 nm in size, created using a Ce4+ precursor, are more effective at removing SiO2 films compared to larger, more crystalline particles from a Ce3+ precursor. This is due to their increased interaction with the SiO2 film during the polishing process, challenging the conventional emphasis on mechanical abrasion in chemical mechanical planarization (CMP) and highlighting the crucial role of chemical interactions. Further analysis through FT-IR and TGA-FTIR techniques showed distinct functional group profiles on the ceria surfaces. Ceria derived from Ce4+ exhibited a higher presence of OH and NO3 groups, enhancing adsorption capabilities, as verified by CHN analysis. Importantly, first-principles calculations identified these surface groups as key to improving adhesion to SiO2 films. Surfaces of amorphous CeO2, rich in -OH and -NO3 groups, showed significantly higher adhesion levels than their crystalline counterparts, connecting crystallinity to chemical functionality. This new insight leads to the possibility of designing next-generation CeO2 abrasives with increased chemical activity.