Characterization and electrochemical performance of CeO2 and Eu-doped CeO2 films as a manganese redox flow battery component

Hexagonal CeO_2 and Eu-doped CeO_2 nanoparticles were obtained using a facile microwave-hydro thermal method under mild conditions and their application towards manganese redox flow battery component were studied. The structural properties were studied by X-ray diffraction and indicate that samples present a fluorite structure. Raman spectroscopy shows Eu3+ ions substitute Ce~(4+) and generate oxygen vacancies. Electrochemical properties of pure and Eu-doped CeO_2 films deposited at graphite substrates investigated by cyclic voltammetry and galvanostatic charge—discharge indicate that dopant concentration affects the electrochemical properties of CeO_2. The increase in the reversibility redox of electrochemical systems observed is attributed to coexistence of Ce~(4+)/Ce~(3+) redox couple confirmed by XPS.Charge—discharge tests display coulombic and voltage efficiency values of above 80% and 90%, respectively. The obtained specific capacity for Ce_(0.99)Eu_(0.01)O_2(372.49 mAh/g) and pure oxide(334.84 mAh/g)indicates that both samples are promising for application in Mn-batteries.     

Effect of samarium and praseodymium addition on water gas shift performance of Co/CeO2 catalysts

The performance of Co supported over ceria and doped ceria (by Sm and Pr) catalysts towards the water gas shift reaction was studied for the removal of CO from syngas to produce high purity hydrogen for a fuel cell application. It is found that 1%Co/Ce-5%Sm-O yields the highest catalytic performance towards this reaction compared with undoped-Sm and doped-Pr. An addition of Sm onto ceria support reveals a small crystallite size with high surface area and well dispersed cobalt on ceria surface. Moreover, a presence of Sm increases the reducibility of cobalt species and surface oxygen. The positive effect of Sm on increasing the WGS activity of Co/CeO₂ is because Sm contributes to the reduction of Ce⁴⁺ to Ce³⁺ which gives rise to oxygen vacancies and facilitates the electron movement at the surface leading to an ease of surface reduction.     

Structure and chemical states of highly eptiaxial CeO2（001） films grown on SrTiO_3 substrate by laser molecular beam epitaxy

Highly epitaxial and pure（001）-oriented CeO2 films were grown on SrTiO3（001） substrates by laser molecular beam epitaxy method without any gas ambient.Layer-by-layer epitaxial growth mode of CeO2 was confirmed by in situ reflection high-energy electron diffraction（RHEED） observations.High-resolution X-ray diffraction（HRXRD） and high-resolution transmission electron microscopy（HRTEM） results indicated the STO（100）//CeO2（100）,STO[100]//CeO2 [110] epitaxial relationship for out-of-plane and in-plane,respectively.The formation mechanism of the epitaxial film was also discussed in the light of a theoretical model.Chemical states of the LMBE ceria films were evaluated and evidences for the existence of Ce3＋and oxygen vacancies were presented.     

Promotional effect of CO pretreatment on CuO/CeO2 catalyst for catalytic reduction of NO by CO

The CuO/CeO2 catalysts were investigated by means of X-ray diffraction(XRD),laser Raman spectroscopy(LRS),X-ray photoelectronic spectroscopy(XPS),temperature-programmed reduction(TPR),in situ Fourier transform infrared spectroscopy(FTIR) and NO+CO reaction.The results revealed that the low temperature(150 °C) catalytic performances were enhanced for CO pretreated samples.During CO pretreatment,the surface Cu+/Cu0 and oxygen vacancies on ceria surface were present.The low valence copper species activated the adsorbed CO and surface oxygen vacancies facilitated the NO dissociation.These effects in turn led to higher activities of CuO/CeO2 for NO reduction.The current study provided helpful understandings of active sites and reaction mechanism in NO+CO reaction.     

One-step solution combustion synthesis of micro-nano-scale porous Cu/CeO2 with enhanced photocatalytic properties

The Cu/CeO₂ nanoporous composite material was prepared via a one-step and energy-saving method of solution combustion synthesis(SCS).The phase composition,surface morphology and optical characteristics of Cu/CeO₂ were studied.The results show that the SCS products are composed of cubic fluorite CeO₂ and Cu.Due to the generation and escape of gas during the synthetic reaction,the SCS CeO₂ shows porous structure,in which the mesopores(diameter 10-17 nm) ...     

Ce(Ⅲ)-modulation over non-enzymatic Pt/CeO2/GO biosensor with outstanding sensitivity and stability for lactic acid detection

A series of non-enzymatic graphene functionalized biosensors was developed via deposition precipitation method for lactic acid(LA) detection,which we re characterized by transmission electron micro scopy(TEM),Raman spectroscopy,X-ray photoelectron spectroscopy(XPS),gas chromatography-mass spectrometry,liquid chromatography-mass spectro metry,and proton nuclear magnetic re sonance(¹H NMR).The electrochemical performances of the non-enzymatic biosensors were measured by means of the ele...     

3D ball-type self-assemble CeO2 nanostructure produced by facile hydrothermal strategy for catalytic wet air oxidation of N,N-dimethylformamide

CeO₂ plays an important role in heterogeneous catalysis,and its performance is highly dependent on the oxygen vacancies and surface defects,which can be easily tuned by manipulating the particle dimensions and morphology.In this article,we report a facile strategy to synthesize a new type of CeO₂ with modified surface property which can improve its ability to active oxygen.The obtained ball-type 3D selfassemble CeO₂(M-CeO₂) is composed of large amounts...     

Synthesis of CeO_2/fly ash cenospheres composites as novel photocatalysts by modified pyrolysis process

A novel fly ash cenospheres(FACs)-supported CeO2 composite(CeO2/FACs) was successfully synthesized by the modified pyrolysis process.The prepared composites were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS), and diffuse reflection spectra(DRS) techniques.XRD results indicated that the CeO2 film coated on cenospheres was a face-centered cubic structure.SEM images confirmed that the CeO2 film was relatively compact.XPS results showed that Ce was present as both Ce4+ and Ce3+ oxidation states in CeO2 film coated on FACs substrate.The bandgap of the composite was narrower compared with the pure CeO2.The as-prepared material exhibited good photocatalytic activity for the decolorization of methylene blue(MB) under visible light irradiation, and the first-order reaction rate constant(k) of 0.0028 min–1 for CeO2/FACs composite was higher than 0.0015 min–1 of pure CeO2.The fact that they floated on water meant that CeO2/FACs composites were easily recovered from water by filtration after the reaction.The recycling test revealed that the composites were quite stable during the MB photocatalytic decolorization.The CeO2/ FACs catalyst was therefore promising for practical use in the degradation of pollutants or water cleanup.     

Constructing a high concentration CuO/CeO2 interface for complete oxidation of toluene: The fantastic application of spatial confinement strategy

In this paper,CeO₂ substrate was prepared by the sol-gel method,further CuO was introduced by adding the copper complexes with chelating agents into the sol-gel precursors of CeO₂,in which different chelating agents(β-cyclodextrin,glucose and trimesic acid) were tried.This synthesis method helps the CuO species to disperse very uniformly in the CeO₂ substrates.When the amount of copper oxide is up to33 mol%,the CuO/CeO₂ samples can still maintain a hig...     

Effect of CuO species and oxygen vacancies over CuO/CeO2 catalysts on low-temperature oxidation of ethyl acetate

The catalytic oxidation of ethyl acetate(EA) was studied over CuO/CeO₂ catalysts which were prepared by ball milling with different precursors(copper oxide,cerium acetate,cerium dioxide,copper acetate and cerium hydroxide).The CuO/CeO₂ catalyst(O-A) prepared with copper oxide and cerium acetate as precursors shows very high catalytic activity that 100% EA conversion is achieved at low temperature of 220℃.It is found that specific surface area(112.8 m²/g),particle...     

Regulating local coordination environment of rhodium single atoms in Rh/CeO2 catalysts for N2O decomposition

Rh single atom catalysts(SACs) have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the development and application of Rh SACs,there are few reports on the precise control of the local coordination environment of Rh single sites on CeO₂ and their catalytic performance for N₂O decomposition.Herein,Rh/CeO₂ catalysts with different Rh-O coordin...     

Performance of mesoporous CeO2-Cr2O3 mixed metal oxides applied to benzene catalytic combustion

In this paper,a hydrothermal method was used to prepare(Ce,Cr)-MOF with different Ce/Cr molar ratios and then a series of CeO₂-Cr₂O₃ mixed metal oxides(CeCr-MMO) with mesoporous structure were prepared by thermal decomposition of these MOFs at different temperatures.After a series of characterization techniques were applied to test the physicochemical properties of the materials,it is found that thermal decomposition temperature(TDT) and Ce/Cr molar ratios have i...     

Influences of CeO2 morphology on enhanced performance of electro-Fenton for wastewater treatment

As a kind of rare-earth oxide, CeO₂ has been considered as a great potential material for its abundant oxygen vacancies and catalysis activity in wastewater treatment. In this study, three ceria samples with different morphological structure were prepared, and their effect on contaminates degradation in electro-Fenton (E-Fenton) system was investigated. It is found that the morphology of CeO₂ has great influence on promoting the performance of E-Fenton process. The rod-like CeO₂ (R–CeO₂) induced E-Fenton system shows higher azo dye X3B removal and mineralization rates than cubs (C–CeO₂) and octahedrons (O–CeO₂), and the degradation kinetic rate constants are 0.28, 0.169 and 0.181 min^?1 respectively, already surpass that of the blank one (0.120 min^?1). The H₂O₂ generation capacity of R–CeO₂ induced E-Fenton system is also superior to the others, and the corresponding Faraday current efficiency even increases to 166.2% at 2.5 min. Characterizations by scanning-transmission electron microscopy (STEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron spin resonance (ESR), Raman spectroscopy were conducted to disclose the mystery behind this phenomenon. The results indicate that the difference of surface oxygen vacancy density in different shaped CeO₂ acts as a magic driving force for the accelerated oxygen reduction, and then leads to the enhanced degradation efficiency of E-Fenton system. This work provides a new insight into the development and application of rare-earth elements based catalyst in E-Fenton technology.     

Catalytic feasibility of Ce-doped LaCoO3 systems for chlorobenzene oxidation: An analysis of synthesis method

A family of Ce-doped LaCoO₃ perovskites are presented as possible catalysts for Cl–VOCs elimination. These materials with different contents of Ce were obtained through the citrate and the reactive grinding methods. The insertion of Ce in the original perovskite structure favours the presence of Co²⁺/Co³⁺ and Ce³⁺/Ce⁴⁺ redox pairs and a higher content of oxygen vacancies that enhances the catalytic performance in chlorobenzene combustion based on differential kinetics studies. The family obtained by the grinding method presents a performance as high as that synthesized by citrate method. Thus, the reactive grinding is a feasible green chemistry alternative to obtain a catalyst with the same performance as that obtained from traditional methods. Finally, the stability of samples was evaluated under total combustion reaction conditions showing an excellent activity during 45 h time on stream.     

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 Al_91.3Ce₈Rh_0.7 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.     

Ce1–xSmxO2–δ-attapulgite nanocomposites：synthesis via simple microwave approach and investigation of its catalytic activity

Ce1–x Smx O2–δ-attapulgite（ATP） nanocomposites were successfully prepared via a facile microwave approach.This was a facile and rapid process requiring only low power of microwave irradiation（160 W）.The catalytic performance of the Ce1–x Smx O2–δ-ATP nanocomposites with different Sm contents for degradation of methylene blue（MB） was systematically evaluated.The Ce1–x Smx O2–δ-ATP nanocomposites showed enhanced catalytic activities compared with pure CeO2/ATP.Specifically,the catalytic activities of Ce1–x Smx O2–δ-ATP nanocomposites increased with increase in Sm content from x=0.0 to 0.3.The introduction of an optimal amount of Sm3＋into CeO2 contributed to the formation of structure defects and electronic defects in the oxide lattice,which could increase concentration of oxygen vacancies.However,further increasing Sm content to x=0.4 induced the formation of more agglomerates,leading to decreased catalytic activity.It was believed that this facile,rapid microwave-assisted strategy was scalable and could be applied to synthesize other nanocomposites for different applications.     

Promoting effect of microwave irradiation on CeO_2-TiO_2 catalyst for selective catalytic reduction of NO by NH_3

In this work we prepared several CeO₂-TiO₂ catalysts for the NH₃-SCR reactionusing co-precipitation with assistance of microwave irradiation. The catalytic NH₃-SCR activities over CeO₂-TiO₂ catalysts at low temperatures are largely enhanced by the treatment of microwave irradiation, the operation temperature window is also broadened. For better understanding the promotion mechanism, the catalyst prepared by conventional co-precipitation with and without microwave irradiation treatment was characterized with H₂-TPR, NH₃-TPD, XPS, XRD and BET. Microwave irradiation treatment accelerates the crystallite rate of CeO₂-TiO₂ catalysts, and greatly enlarges their surface area by adjusting their microstructures. The resistance to SO₂ and H₂O is also improved via regulating the hierarchical pore structure by the microwave irradiation. Microwave irradiation treatment can also improve the redox property and increase the acid sites over the catalyst surfaces. The result of in situ DRIFTS suggests that the microwave irradiation treatment generates more Brønsted acid sites on CeO₂-TiO₂-2 h catalyst, helpful in SCR reactions. XPS results show that after microwave irradiation on the CeO₂-TiO₂ catalysts, the surface demonstrates an elevated concentration of chemisorbed oxygen, consequently leading to better oxidation of NO to NO₂. Additionally, the molar ratio of Ce³⁺/Ce⁴⁺ has been elevated after being treated by microwave irradiation, a vital factor in enhancing the NH₃-SCR activities.     

Ln3+ (Ln = Eu,Dy) - doped Sr2CeO4 fine phosphor particles: Wet chemical preparation,energy transfer and tunable luminescence

The Sr₂CeO₄:Ln³⁺ (Ln = Eu, Dy) fine phosphor particles were prepared by a facile wet chemical approach, in which the consecutive hydrothermal-combustion reaction was performed. The doping of Ln³⁺ into Sr₂CeO₄ has little influence on the structure of host, and the as-prepared samples display well-crystallized spherical or elliptical shape with an average particle size at about 100–200 nm. For Eu³⁺ ions-doped Sr₂CeO₄, with the increase of Eu³⁺-doping concentration, the blue light emission band with the maximum at 468 nm originating from a Ce⁴⁺ → O²⁻ charge transfer of the host decreases obviously and the characteristic red light emission of Eu³⁺ (⁵D₀→⁷F₂ transition at 618 nm) is enhanced gradually. Simultaneously, the fluorescent lifetime of the broadband emission of Sr₂CeO₄ decreases with the doping of Eu³⁺, indicating an efficient energy transfer from the host to the doping Eu³⁺ ions. The energy transfer efficiency from the host to Eu³⁺ was investigated in detail, and the emitting color of Sr₂CeO₄:Eu³⁺ can be easily tuned from blue to red by varying the doping concentration of Eu³⁺ ions. Moreover, the luminescence of Dy³⁺-doped Sr₂CeO₄ was also studied. Similar energy transfer phenomenon can be observed, and the incorporation of Dy³⁺ into Sr₂CeO₄ host leads to the characteristic emission of ⁴F_9/2 → ⁶H_15/2 (488 nm, blue light) and ⁴F_9/2 → ⁶H_13/2 (574 nm, yellow light) of Dy³⁺. The Sr₂CeO₄:Ln³⁺ fine particles with tunable luminescence are quite beneficial for its potential applications in the optoelectronic fields.     

The free energy of formation of Ce2O2S and the nonstoichiometry of cerium oxides

The free energy of formation of Ce₂O₂S was determined by equilibrating CeO₂with COCO₂-SO₂ gas mixtures in the temperature range 900 to 1400°C. There was no significant sulfur solubility in cerium oxide and the free energy of formation of Ce₂O₂S was considerably less than previously estimated; it is 12 kcal (50 kJ) lower at 1300°C The oxygen dissociation pressures for the nonstoichiometric cerium oxide was also measured by equilibrating CeO₂ with CO-CO₂ gas mixtures in the temperature range 1000 to 1450°C and oxygen pressures from 10^-6 to 10^-18 atm. The results indicate a very large range of nonstoichiometry from CeO₂ to at least CeO_1.72. The new thermodynamic information was used to estimate the phase equilibria for the Fe-Ce-S-O system. The calculations indicate that for a steel with normal sulfur levels treated with aluminum and rare earth deoxidizers very little Ce₂O₃will form but rather Ce₂O₂S or cerium Sulfides. Also the stability range of Ce₂O₂S is smaller than previously believed.     

Facile synthesis of nanoceria by a molten hydroxide method and its photocatalytic properties

Ceria nanoparticles were facilely synthesized by a molten NaOH-KOH hydroxide flux method with the precursor of Ce(NO_3)_3·6H_2O under different conditions in alumina crucibles or Teflon-lined stainless steel autoclave.The XRD patterns and TEM images show that both the crystal and particle sizes of synthesized nanoceria are around 10 nm.XPS results reveal that the nanoceria obtained in alumina crucible has a Ce~(3+) fraction of 17.1% which is higher than that of ceria synthesized in the Teflon vessel,the FTIR spectra of nanoceria prepared in alumina crucible show a stronger intensity of O-H stretching mode.UV-DRS and PL spectra results show that the nanoceria synthesized in alumina crucible with a calculated band gap of 2.9 eV has a wider responding light wavelength and a lower photogene rated electron-hole recombination rate,due to a higher concentration of oxygen vacancies(Ce~(3+)%).The photocatalytic results show that the degradation ratio and rate of the Rhodamine B(RhB) solution with the nanoceria synthesized in alumina crucible are 98.39% and 0.02919 min~(-1),both of which are larger than those of the ceria obtained from Teflon vessel.This method proves to be a simple and scalable way to synthesize nanoceria with rich oxygen vacancies and high photocatalytic activity.