Oxygen Vacancies In CeO2 Research Articles

Improved HER/OER Performance of NiS2/MoS2 Composite Modified by CeO2 and LDH.

In recent years, there has been significant interest in transition-metal sulfides (TMSs) due to their economic affordability and excellent catalytic activity. Nevertheless, it is difficult for TMSs to achieve satisfactory performance due to problems such as low conductivity, limited catalytic activity, and inadequate stability. Therefore, a catalyst with a heterostructure constituted of a nickel-iron-layered double hydroxide, nickel sulfide, molybdenum disulfide, and cerium dioxide was designed. At the current density of 10 mA cm-2 in an alkaline solution, the catalyst exhibits a HER overpotential of 116 mV. In addition, an overpotential of 235 mV@150 mA cm-2 was displayed for OER. The catalyst showed a good retention rate (94.7% for HER, 98.6% for OER) after 160 h stability tests. The excellent electrochemical performance is attributed to the following points: 1. The self-supporting three-dimensional hierarchical structure provides abundant sites, fast ion diffusion channels, and electron transfer paths, and ensures structural stability. 2. The strong interfacial electron interaction between Ni3S2/MoS2 heterojunction and NiFe-LDH improves the OER reaction kinetics. 3. The Ce3+ and oxygen vacancies in CeO2 promote the dissociation of H2O and promote the HER reaction kinetics. This approach paves the way for developing highly efficient electrocatalysts for various electrochemical applications.

Directional Growth and Density Modulation of Single‐Atom Platinum for Efficient Electrocatalytic Hydrogen Evolution

AbstractDispersion of single atoms (SAs) in the host is important for optimizing catalytic activity. Herein, we propose a novel strategy to tune oxygen vacancies in CeO2−X directionally anchoring the single atom platinum (PtSA), which is uniformly dispersed on the rGO. The catalyst's performance for the hydrogen evolution reaction (HER) can be enhanced by controlling different densities of CeO2‐X in rGO. The PtSA performs best optimally densified and loaded on homogeneous and moderately densified CeO2‐X/rGO (PtSA−M−CeO2−X/rGO). It exhibited higher activity in HER with an overpotential of 25 mV at 0.5 M H2SO4 and 33 mV at 1 KOH than that of almost reported electrocatalysts. Furthermore, it exhibited stability for 90 hours at −100 mA cm−2 in 1 KOH and −150 mA cm−2 in 0.5 M H2SO4 conditions, respectively. Through comprehensive experiments and theoretical calculations, the suitable dispersion density of PtSA on the defects of CeO2−X with more active sites gives the potential for practical applications. This research paves the way for developing single‐atom catalysts with exceptional catalytic activity and stability, holding promise in advanced green energy conversion through defects engineering.

Rationally controlling interfaces and oxygen vacancies of CeO2@C core–shell nanorods/nanofibers for superior microwave absorption and thermal conduction

High-performance thermally conductive-microwave absorbing integrated materials are highly required to mitigate the severe electromagnetic pollution and overheating generated in electronic devices. However, the incompatibility between thermal conduction and microwave absorption impedes their collaborative development. Herein, an adjustment strategy for interface- and oxygen-vacancy-linkage was adopted to rationally construct CeO2@C core–shell nanorods/nanofibers (CSNRs/NFs) and cooperatively boost their electrical, thermal, and microwave absorption properties. A hydrothermal-annealing technique was employed to synthesize CeO2@C CSNRs/NFs. Their core–shell structure, oxygen vacancies/lattice defects, and length-to-diameter ratio were accurately adjusted by changing the annealed temperature (Ta) and toluene volume (V). The CeO2@C CSNRs/NFs produced under Ta = 600 °C and V = 1.5 mL exhibit high thermal conductivity (TC = 2.94 W/(m·K)) at a small load of 40 wt%. The large TC is mainly due to the weak phonon defect/interface scattering and electron/phonon co-transfer in a 3D continuous path consisting of a 1D structure. Furthermore, the CeO2@C CSNRs/NFs display strong microwave absorption (EABmax/d = 3.27 GHz/mm; RLmin=− 50.98 dB) due to their various polarizations, tunable conduction loss, and multiple internal reflections. These results demonstrate that the CeO2@C CSNR/NFs are an ideal multifunctional material that protects against concurrent EM interference and excess heat in electronic packaging materials.

The Effect of Precursor Concentration on the Crystallite Size of CeO2 to Enhance the Sulfur Resistance of Pt/CeO2 for Water Gas Shift

To develop customized sulfur–resistant catalysts for the water gas shift (WGS) reaction in the waste–to–hydrogen process, the effects of changing the nucleation conditions of the CeO2 support on catalytic performance were investigated. Supersaturation is a critical kinetic parameter for nuclei formation. The degree of supersaturation of the CeO2 precipitation solution was controlled by varying the cerium precursor concentration from 0.02 to 0.20 M. Next, 2 wt.% of Pt was impregnated on those various CeO2 supports by the incipient wetness impregnation method. The prepared samples were then evaluated in a WGS reaction using waste–derived synthesis gas containing 500 ppm H2S. The Pt catalyst supported by CeO2 prepared at the highest precursor concentration of 0.20 M exhibited the best sulfur resistance and catalytic activity regeneration. The sulfur tolerance of the catalyst demonstrated a close correlation with its oxygen storage capacity and easier reducibility. The formation of oxygen vacancies in CeO2 supports is promoted by the formation of small crystals due to a high degree of supersaturation.

Adjusting active sites and metal-support interactions of ceramic-loaded Pd/P-CeO2-Al2O3 coating to optimize CO2 methanation pathways

Adjusting the active sites and metal-support interactions (MSI) of catalytic coatings on foam ceramics is a desirable strategy to improve CO2 methanation performance. By using a three-dipping and one-roasting technique, a highly active Pd/P-CeO2-Al2O3 catalyst (HA-Pd/PCA) with uniform three-dimensional mesh-like pores and daisy-like clusters was created. As PdO that was embedded in oxygen vacancies of CeO2 was reduced, oxygen vacancies were released. Pd then interacted with lattice oxygen close to the oxygen vacancies to create a strong MSI effect in the form of electron transfer. This translates to better Pd dispersion and more effective activation of the hydrogen. Moreover, the path of the hydrogen spillover that was necessary to hydrogenate the CO2 adsorbed in oxygen vacancies was shortened. In terms of the presence of acid-base sites, oxygen species, and oxygen vacancies, HA-Pd/PCA provided significant advantages. Based on this, the rate of carbonate to formate increased and the conversion pathway changed from a single bidentate formate to a dual pathway comprising bidentate formate and monodentate formate. The consumption and regeneration of hydroxyl groups were kept in balance. The outcomes demonstrated that HA-Pd/PCA had ideal stability, 100 % CH4 selectivity, and 86 % CO2 conversion.

Elucidating the Role of Surface Ce4+ and Oxygen Vacancies of CeO2 in the Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol.

Cerium dioxide (CeO2) was pretreated with reduction and reoxidation under different conditions in order to elucidate the role of surface Ce4+ and oxygen vacancies in the catalytic activity for direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol. The corresponding catalysts were comprehensively characterized using N2 physisorption, XRD, TEM, XPS, TPD, and CO2-FTIR. The results indicated that reduction treatment promotes the conversion of Ce4+ to Ce3+ and improves the concentration of surface oxygen vacancies, while reoxidation treatment facilitates the conversion of Ce3+ to Ce4+ and decreases the concentration of surface oxygen vacancies. The catalytic activity was linear with the number of moderate acidic/basic sites. The surface Ce4+ rather than oxygen vacancies, as Lewis acid sites, promoted the adsorption of CO2 and the formation of active bidentate carbonates. The number of moderate basic sites and the catalytic activity were positively correlated with the surface concentration of Ce4+ but negatively correlated with the surface concentration of oxygen vacancies. The surface Ce4+ and lattice oxygen were active Lewis acid and base sites respectively for CeO2 catalyst, while surface oxygen vacancy and lattice oxygen were active Lewis acid and base sites, respectively, for metal-doped CeO2 catalysts. This may result from the different natures of oxygen vacancies in CeO2 and metal-doped CeO2 catalysts.

Assisting Ni catalysis by CeO2 with oxygen vacancy to optimize the hydrogen storage properties of MgH2

Although MgH2 has been widely regarded as a promising material for solid-state hydrogen storage, its high operating temperature and slow kinetics pose a major bottleneck to its practical application. Here, a nanocomposite catalyst with interfacial coupling and oxygen defects, Ni/CeO2, is fabricated to promote H2 desorption and absorption properties of MgH2. The interface of Ni/CeO2 contributes to both strong mechanical coupling towards stabilizing partial Ni and electronic coupling towards inducing a high concentration of oxygen vacancies in CeO2. Theoretical calculations evidence that CeO2 with oxygen vacancy assist Ni in weakening the energy of Mg-H bond as well as enhancing the adsorption energy of Ni upon hydrogen atoms, and the extent of this assistance surprisingly increases with increasing oxygen vacancies concentration. As a result, an impressive performance is achieved by MgH2-5 wt.% Ni/CeO2 with onset desorption temperature of only 165 °C, and it absorbs approximately 80% hydrogen in just 800 s at 125 °C. The generation mechanism of intermediate active species concerning Ni/CeO2 in different states has been analyzed for the first time, and the relationship between interfacial coupling and phase evolution has been elucidated. Therefore, a mechanism of the catalysis-assisting effect regarding oxygen defects is proposed. It is believed that this work provides a unique perspective on the mechanism of interfacial coupling and the generation of defects in composite catalysts.

CeO2 promotes electrocatalytic formic acid oxidation of Pd-based alloys

Engineering metal/oxide interface and controlling composition are the important strategies that aim towards obtaining efficient Pd-based electrocatalysts (ECs). Rationally designed ECs for dehydrogenation of formic acid play a dynamic role in the proper utilization of its chemical energy. Herein, we report Pd3M alloy nanoparticles anchored on CCeO2 (Pd3M/CCeO2, M = Cu, Ni, Co) which shows significant performance towards formic acid oxidation (FAO). Interestingly, Pd3M/CCeO2 (M = Cu, Ni, Co) ECs displayed the best FAO activity via the “dehydrogenation” pathway. The remarkable performance can be mainly attributed to the proper electronic and synergistic effects between Pd and the alloyed metal, which leads to Pd lattice contraction and downshift of d-band center. It was also observed that the FAO activity of Pd3Cu/CCeO2 is superior to that of Pd3Co/CCeO2 and Pd3Ni/CCeO2. The oxygen vacancies in CeO2 and strong Pd/CeO2 interactions established by computational and experimental studies contribute towards the overall electrocatalytic behaviour.

Co/CeO2/C composites derived from bimetallic metal-organic frameworks for efficient microwave absorption.

CeO2, an n-type semiconductor material, has been widely used in microwave absorption (MA) due to its unique structural features such as oxygen vacancies and interstitial atoms. In this paper, Co/CeO2/C composites were prepared by a hydrothermal method followed by a pyrolysis process. The effect of different pyrolysis temperatures (650-950 °C) on the MA property of the composites was investigated. When the pyrolysis temperature was 850 °C, the Co/CeO2/C-850 composite exhibited outstanding MA behavior in the frequency range of 2-18 GHz, displaying a minimum reflection loss (RLmin) of -45.22 dB and an effective absorption bandwidth (EAB) of 4.61 GHz at a thin thickness of 1.75 mm. The MA performance of the Co/CeO2/C composites is mainly attributed to the dielectric loss due to interfacial polarization originating from different interfaces and dipole polarization caused by the oxygen vacancies in CeO2. In addition, the introduction of Co nanoparticles not only provides the magnetic loss but also modulates impendence matching for the current magnetoelectric coupling system.

Increased Oxygen Vacancies in CeO2 for Improved Electrocatalytic Nitrogen Reduction Performance.

Electrochemical nitrogen fixation is a sustainable and economical strategy to produce ammonia. However, fabricating efficient electrocatalysts for nitrogen fixation is still challenging. Theoretical predictions prove that the oxygen vacancy is able to modulate the electronic state of CeO2 and enhance its electrical conductivity, thus promoting the electrochemical nitrogen reduction reaction (NRR) process. Herein, CeO2 with high oxygen vacancy concentration was prepared via a two-step pyrolysis strategy of Ce metal-organic frameworks (MOFs, denoted H-CeO2). Compared to CeO2 with low oxygen vacancy concentration synthesized via one-step pyrolysis of Ce-MOFs (denoted L-CeO2), H-CeO2 exhibits a large NH3 yield rate (25.64 μg h-1 mgcat-1 at -0.5 V vs reversible hydrogen electrode, RHE) and high faradaic efficiency (FE, 6.3% at -0.4 V vs RHE).

Surface Reconstruction of Co4N Coupled with CeO2 toward Enhanced Alkaline Oxygen Evolution Reaction.

Constructing the active interface in a heterojunction electrocatalyst is critical for the electron transfer and intermediate adsorption (O*, OH*, and HOO*) in alkaline oxygen evolution reaction (OER) but still remains challenging. Herein, a CeO2/Co4N heterostructure is rationally synthesized through the direct calcination of Ce[Co(CN)6], followed by thermal nitridation. The in situ electrochemically generated CoOOH on the surface of Co4N serves as the active site for the OER, and the coupled CeO2 with oxygen vacancy can optimize the energy barrier of intermediate reactions of the OER, which simultaneously boosts the OER performance. Besides, electrochemical measurement results demonstrate that oxygen vacancies in CeO2 and optimized absorption free energy originating from the electron transfer between CeO2 and CoOOH contribute to enhanced OER kinetics. This work provides new insight into regulating the interface heterostructure to rationally design efficient OER electrocatalysts under alkaline conditions.

Origin of the low formation energy of oxygen vacancies in CeO2

Oxygen vacancies play a crucial role in determining the catalytic properties of Ce-based catalysts, especially in oxidation reactions. The design of catalytic activity requires keen insight into oxygen vacancy formation mechanisms. In this work, we investigate the origin of oxygen vacancies in CeO2 from the perspective of electron density via high-energy synchrotron powder x-ray diffraction. Multipole refinement results indicate that there is no obvious hybridization between bonded Ce and O atoms in CeO2. Subsequent quantitative topological analysis of the experimental total electron density reveals the closed-shell interaction behavior of the Ce–O bond. The results of first-principles calculation indicate that the oxygen vacancy formation energy of CeO2 is the lowest among three commonly used redox catalysts. These findings indicate the relatively weak bond strength of the Ce–O bond, which induces a low oxygen vacancy formation energy for CeO2 and thus promotes CeO2 as a superior catalyst for oxidation reactions. This work provides a new direction for design of functional metal oxides with high oxygen vacancy concentrations.

Comparison study of preferential oxidation of CO over nanocrystalline Cu/CeO2 catalysts synthesized by different preparation methods

Preferential oxidation of carbon monoxide in presence of excess hydrogen is a promising alternative to restrict the CO deposition in the Pt-anode in the practical polymer electrolyte membrane fuel cell application. In the present work, nanocrystalline copper-ceria catalysts have been synthesized by hydrothermal method, wet impregnation method and urea nitrate combustion method. Their characterizations have been carried out by using X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy . It has been found that Cu 2+ replaced Ce 4+ in cerium oxide, creating oxygen vacancy. The formation of more nano-sized CeO 2 leads to more oxygen vacancies in CeO 2 through the formation of interfacial Cu 1+ ions, which also enhances the CO oxidation activity. Among the synthesized Cu-CeO 2 catalysts, the catalyst prepared by hydrothermal method have shown both CO conversion and CO 2 selectivity as 100% towards CO oxidation at 373 K in the presence of excess H 2 making this catalyst viable for practical fuel cell application.

Constructing heterostructure of CeO2/WS2 to enhance catalytic activity and stability toward hydrogen generation

Transition metal disulfides (TMD) are considered as promising catalysts for hydrogen evolution reaction (HER) due to their unique structural and electronic properties. However, as a representative, the tungsten disulfide (WS 2 ) shows an insufficient HER performance and is still needed to be further improved. Herein, we report the synthesis of CeO 2 -modified WS 2 nanosheets with abundant heterostructures on carbon cloth (CeO 2 /WS 2 /CC) as an efficient self-supported integral electrode for HER. Experimental results and theoretical calculations imply that the intimate electronic interaction between CeO 2 and WS 2 promotes the production of more oxygen vacancies in CeO 2 to regulate the electronic structure of WS 2 , endowing extra active sites, high electron transfer efficiency, and downshifted d-band center of W, which can lead to thermoneutral hydrogen adsorption Gibbs free energies (ΔG H* ) and thus boosts HER. The optimized CeO 2 /WS 2 /CC electrode displays an improved HER performance with an overpotential of 128 mV at 10 mA cm −2 in 0.5 M H 2 SO 4 aqueous solution, 87 mV smaller than that of the WS 2 /CC electrode. Meanwhile, it also could maintain a 20 h of stable HER activity. Our work provides an effective approach to achieve various hybrid catalysts of rare earth compounds-transition metal compounds with highly active sites for superior electrocatalysis. • A monolithic CeO 2 /WS 2 /CC electrode with heterostructure of CeO 2 /WS 2 is fabricated. • The hybrid CeO 2 /WS 2 nanosheets structure is beneficial to exposing more active sites. • The electronic interaction between WS 2 and CeO 2 results in a superior HER activity. • The mechanism of HER over CeO 2 /WS 2 /CC electrode is clarified by DFT calculations.

Increasing oxygen vacancies in CeO2 nanocrystals by Ni doping and reduced graphene oxide decoration towards electrocatalytic hydrogen evolution

A good-performance and low-cost electrocatalyst Ni–rGO/CeO2 has been achieved due to the increased oxygen vacancies and active sites brought about by the synergistic effect of rGO decoration and Ni doping.

Regulating superoxide radicals and light absorption ability for enhancing photocatalytic performance of MoS2@Z by CeO2 rich in adsorbed oxygen

Nano molybdenum disulfide (Nano-MoS2) can be as a photocatalyst for antibiotic removal under visible light. However, the low energy of visible light and limited radicals restrict the applications of nano-MoS2. In this study, ceria dioxide (CeO2) rich in adsorbed oxygen was introduced into MoS2@Z (MoS2@Zeolite) to synthesize full-spectrum CeO2/MoS2@Z photocatalysts (CeO2/MoS2@Zs). The CeO2/MoS2@Z-3 (Ce: 1.5 mmol; Mo: 3.5 mmol) shows the best photocatalytic ability (98.32%) for tetracycline within 150 min, which is 18.20% improvement over MoS2@Z. The UV–vis diffuse reflection spectra of photocatalysts shows that the ultraviolet absorption ability of CeO2/MoS2@Z-3 improved when CeO2 was introduced. The active species trapping experiment and electron paramagnetic resonance (EPR) test prove h+ and superoxide radicals (•O2−) are the main active species, and CeO2 rich in adsorbed oxygen improves the amounts of •O2− in photocatalytic process. Moreover, singlet oxygen (1O2), producing by oxygen vacancies of CeO2, also plays an important role. The enhanced photocatalytic activity is attributed to full-spectrum (200 nm–800 nm) absorption performance, improved content of •O2−, and electron-hole (e−/h+) pairs separation. After five times recycle, the photodegradation efficiency of CeO2/MoS2@Z-3 only decreased by 2.59%. Meantime, the proposed three photocatalytic pathways show that tetracycline eventually degraded into small organics (like C5H8O3), H2O and CO2 by dehydration, demethylation, deamination, dihydroxylation, deamidation, ring-opening reaction and carbonylation. The results show that CeO2/MoS2@Z-3 may become a high efficiency, stable, and promising photocatalyst for tetracycline wastewater treatment.

Effect of the Oxygen Vacancies in CeO2 by the Ce3+ Incorporation to Enhance the Photocatalytic Mineralization of Phenol

AbstractIn this paper, the phenol mineralization by Ce3+‐doped CeO2 by photocatalysis at room temperature, is shown for the first time. The photocatalytic behavior of CeO2 was improved through the incorporation of Ce3+ into its crystalline lattice. The materials were prepared by the precipitation method at low temperatures varying the Ce4+:Ce3+ molar ratio of the precursors during the synthesis process. It is worth noting that, the synthesized photocatalysts did not carry out a thermal treatment after their preparation. The results obtained from Raman analysis demonstrated the formation of oxygen vacancies by the incorporation of Ce3+. The improvement of the photocatalytic activity was attributed to an optimal content of Ce3+ which promoted structural defects (such as oxygen vacancies). Radical species, such as O2.−, are mainly formed during the photocatalytic process, which are probably the main responsible for inducing the mineralization process of the studied pollutant.

Rh/CeO2 composites prepared by combining dealloying with calcination as an efficient catalyst for CO oxidation and CH4 combustion

In this paper, a series of Rh/CeO2 catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pure O2. The effects of the Rh content and calcination temperature on CO oxidation and CH4 combustion were studied, and the results reveal that the Rh/CeO2 catalysts produced by dealloying melt-spun Al91.3Ce8Rh0.7 alloy ribbons and then calcining at 500 °C exhibit the best catalytic activity, the reaction temperatures for the complete conversion of CO and CH4 are as low as 90 and 400 °C, respectively. Furthermore, after 150 h of continuous testing at high concentrations of H2O and CO2, the nature of the catalyst is not irreversibly destroyed and can still return to its initial level of activity. This excellent catalytic activity is attributed to a portion of Rh being uniformly distributed on the CeO2 nanorod surface in the form of nanoparticles, forming strong Rh–CeO2 interfacial synergy. Another portion of Rh permeated into the CeO2 lattice, which results in a significant increase in the number of oxygen vacancies in CeO2, thus allowing more surface active oxygen to be adsorbed and converted from the gas phase. Moreover, the catalytic reaction can proceed even in an oxygen-free environment due to the excellent oxygen storage performance of the Rh/CeO2 catalyst.

Characterization of the inhomogeneity of Pt/CeO x /Pt resistive switching devices prepared by magnetron sputtering

There are unrevealed factors that bring about the performance variations of resistive switching devices. In this work, Pt/CeO x /Pt devices prepared by magnetron sputtering showed rectification in their asymmetrical current–voltage (I–V) curves during voltage sweeps. X-ray photoelectron spectroscopy showed that the deposited CeO x film had an inhomogeneous composition, and more oxygen vacancies existed in CeO x near the top electrode. The asymmetrical resistance change of the Pt/CeO x /Pt devices can be explained by the presence of more charged oxygen vacancies in CeO x near the top electrode, along with the Schottky conduction mechanism. This work reveals that the compositional inhomogeneity is inevitable in the magnetron sputtering of oxide targets like CeO2 and can be an important source of device-to-device and cycle-to-cycle variations of memristors.

Oxygen vacancy engineering of cerium oxide for the selective photocatalytic oxidation of aromatic pollutants

The engineering of oxygen vacancies in CeO2 nanoparticles (NPs) allows the specific fine-tuning of their oxidation power, and this can be used to rationally control their activity and selectivity in the photocatalytic oxidation (PCO) of aromatic pollutants. In the current study, a facile strategy for generating exceptionally stable oxygen vacancies in CeO2 NPs through simple acid (CeO2-A) or base (CeO2-B) treatment was developed. The selective (or mild) PCO activities of CeO2-A and CeO2-B in the degradation of a variety of aromatic substrates in water were successfully demonstrated. CeO2-B has more oxygen vacancies and exhibits superior photocatalytic performance compared to CeO2-A. Control of oxygen vacancies in CeO2 facilitates the adsorption and reduction of dissolved O2 due to their high oxygen-storage ability. The oxygen vacancies in CeO2-B as active sites for oxygen-mediated reactions act as (i) adsorption and reduction reaction sites for dissolved O2, and (ii) photogenerated electron scavenging sites that promote the formation of H2O2 by multi-electron transfer. The oxygen vacancies in CeO2-B are particularly stable and can be used repeatedly over 30 h without losing activity. The selective PCOs of organic substrates were studied systematically, revealing that the operating mechanisms for UV-illuminated CeO2-B are very different from those for conventional TiO2 photocatalysts. Thus, the present study provides new insights into the design of defect-engineered metal oxides for the development of novel photocatalysts.