Influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 for NO reduction by CO

In order to investigate the influence of MnO2 modification methods on the catalytic performance of CuO/CeO2 catalyst for NO reduction by CO,two series of catalysts(xCuyMn/Ce and xCu/yMn/Ce) were prepared by co-impregnation and stepwise-impregnation methods,and characterized by means of X-ray diffraction(XRD),Raman spectra,H2-temperature programmed reduction(H2-TPR),in situ diffuse reflectance infrared Fourier transform spectra(in situ DRIFTS) techniques.Furthermore,the catalytic performances of these catalysts were evaluated by NO+CO model reaction.The obtained results indicated that:(1) The catalysts acquired by co-impregnation method exhibited stronger interaction owing to the more sufficient contact among each component of the catalysts compared with the catalysts obtained by stepwise-impregnation method,which was beneficial to the improvement of the reduction behavior;(2) The excellent reduction behavior was conducive to the formation of low valence state copper species(Cu+/Cu0) and more oxygen vacancies(especially the surface synergetic oxygen vacancies(SSOV,Cu+-□-Mn(4–x)+)) during the reaction process,which were beneficial to the adsorption of CO species and the dissociation of NO species,respectively,and further promoted the enhancement of the catalytic performance.Finally,in order to further understand the difference between the catalytic performances of these catalysts prepared by co-impregnation and stepwise-impregnation methods,a possible reaction mechanism(schematic diagram) was tentatively proposed.     

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...     

Preparation and characteristics of nano-crystalline Cu-Ce-Zr-O composite oxides via a green route: supercritical anti-solvent process

The nano-crystalline Cu-Ce-Zr-O composite oxides were successfully prepared by the supercritical anti-solvent (SAS) process. The physicochemical properties and catalytic performances were investigated by X-ray diffraction (XRD), Raman spectroscopy, H2 temperature-programmed reduction (H2 -TPR), oxygen storage capacity (OSC) measurement and catalytic activity evaluation. It was found that Cu2+ ions incorporated into CeO2 -ZrO2 lattice to form Cu-Ce-Zr-O solid solution associated with the formation of oxygen vacancies. The Cu-Ce-Zr-O catalysts prepared via the SAS process with the Cu content 2.63 mol.% showed the highest OSC index of 636.9 μmol/g. Compared with the samples prepared by impregnation method, Cu doping using SAS process could improve the dispersion of Cu2+ in the composite oxide, enhance the interaction between Cu2+ and CeO2-ZrO2 , improve the reducibility of catalyst, and thus improve the OSC performance and increase the catalytic activity for CO oxidation at low temperature.     

Synergistic effect between MnO and CeO2 in the physical mixture：Electronic interaction and NO oxidation activity

MnO and CeO2 powders were mechanically mixed by a spatula and by milling to obtain loose-contact and tight-contact mixed oxides,respectively.The monoxides and their physical mixtures were characterized by X-ray diffraction（XRD）,Brunauer-Emmett-Teller（BET）,X-ray photoelectron spectroscopy（XPS）,Raman,O2 temperature-programmed desorption（O2-TPD）,H2 temperature-programmed reduction（H2-TPR） and NO temperature-programmed oxidation（NO-TPO）.The MnOx-CeO2 solid solutions did not form without any calcination process.The oxidation state of manganese tended to increase while the ionic valence of cerium decreased in the mixed oxides,accompanied with the formation of oxygen vacancies.This long-ranged electronic interaction occured more significantly in the tight-contact mixture of MnO and CeO2.The formation of more Mn4＋and oxygen vacancies promoted the catalytic oxidation of NO in an oxygen-rich atmosphere.     

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...     

Controllable synthesis of argentum decorated CuOx@CeO2 catalyst and its highly efficient performance for soot oxidation

In this paper, CuO_x@Ag/CeO₂ catalysts were synthesized by simple wet-chemical method and equal volume impregnation method. The obtained catalysts were subjected to soot temperature programmed oxidation (soot-TPO) activity tests and were further characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy/high-resolution transmission electron microscopy (TEM/HR-TEM), N₂ physisorption, X-ray photoelectron spectroscopy (XPS) and H₂-temperature programmed reduction (H₂-TPR). The results show that CuO_x@Ag/CeO₂ synthesized presents well controlled core-shell structures, with nano-cube like Cu₂O as the core and Ag decorated polycrystalline CeO₂ grafting layers as the shell. Such core-shell structured CuO_x@Ag/CeO₂ can successfully construct a secondary oxygen delivery channel (CuO_x → CeO₂ → Ag) to effectively transfer bulk oxygen of the catalyst to the soot, resulting in its excellent soot oxidation activity compared to CuO_x@CeO₂. The potential benefiting effect by Ag introduction over Cu@Ag/Ce can be concluded as: (i) pumping lattice oxygen and accelerating gaseous O₂ dissociation to generate significantly increased active surface oxygen content; (ii) modulating a moderate surface oxygen vacancies concentration to maintain more highly active O₂^– species.     

A comparative DFT+U study of CO oxidation on Pd- and Zr-doped ceria

Metal-doped ceria catalysts have been applied in many important catalytic processes.In this work,we performed density functional theory calculations corrected by on-site Coulomb interactions to study the Pd-and Zr-doped CeO₂(111) surfaces with the dopant at different locations.The formation of oxygen vacancies and CO oxidation were systematically calculated on the various doped surfaces.We find that both Pd and Zr doping can activate the surface lattice O and reduce the energy barrier...     

Effect of active oxygen on the performance of Pt/CeO2 catalysts for CO oxidation

This study was focused on the influence of active oxygen on the performance of Pt/CeO_2 catalysts for CO oxidation. A series of CeO_2 supports with different contents of active oxygen were obtained by adding surfactant at different synthesis steps. 0.25 wt% Pt was loaded on these CeO_2 supports by incipientwetness impregnation methods. The catalysts were characterized by N2 adsorption, X-ray diffraction(XRD), high-resolution transmission electron microscopy(HRTEM), H_2 temperature-programmed reduction(H_2-TPR), dynamic oxygen storage capacity(DOSC) and in-situ DRIFTS technologies. For S-f supports, the surfactant was added into the solution before spray-drying in the synthesis process, which facilitates more active oxygen formation on the surface of CeO_2. After loading Pt, the more active oxygen on CeO_2 contributes to dispersing Pt species and enhancing the CO oxidation activity. As for the aged samples,Pt-R-h shows the highest activity above 190 ℃ because of the presence of more partly oxidized Pt~(δ+) species. Thus the activity is also influenced by the states of Pt and the Pt~(δ+) species may contribute to the high activity at elevated temperature.     

A novel ceria hollow nanosphere catalyst for low temperature NOx storage

In this work, a highly active CeO₂ catalyst with hollow nanosphere morphology for low temperature NO_x storage was prepared by a surfactant-assisted solvothermal reaction. The physicochemical properties of ceria samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption–desorption, H₂-temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and in situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The as-prepared CeO₂ nanosphere possesses excellent NO oxidation capacity, smaller mesopores, better reducibility and more surface Ce³⁺ content. Compared with CeO₂ with nanorod and nanoparticle morphologies, CeO₂ nanosphere shows better intrinsic low temperature NO_x trapping performance, with a wide operating temperature window (150–300 °C), high NO_x adsorption capacity (NAC, 640–745 μmol/g) and high NO_x storage capacity (NSC, 250–350 μmol/g). Two reaction pathways are speculated for NO_x adsorption on CeO₂ nanosphere, including “nitrate route” and “nitrite route”. The thermally unstable surface nitrites formed on the CeO₂ nanosphere allow ceria to release more NO_x during the desorption process. The present work provides a new ceria morphology for NO_x traps, which may become a potential excellent NO_x storage material.     

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.     

Barrier effect of SiO_2 shell over hollow CeO_2/CuO@SiO_2 catalysts for broadening temperature window of total CO conversion

The hollow inverse CeO_2/CuO@SiO_2 catalysts with different Ce/Cu mass ratios were synthesized by the two-step hydrothermal and incipient wetness impregnation methods,and characterized by multitechnique characterizations,such as SEM,TEM,XRD,H_2-TPR,XPS and N_2 adsorption-desorption techniques.It is found that the hollow shell is composed of CuO and SiO_2,and CeO_2 nanoparticles are coated on the surface of CuO@SiO_2 support.And the CeO_2/CuO@SiO_2 catalyst with the Ce/Cu mass ratios of 1:1 denoted as 1 CeO_2/CuO@SiO_2,which possesses a maximum amount of highly dispersed copper species and medium-sized CuO as well as the highest concentration of oxygen vacancies,exhibits the highest catalytic activity and widest full CO conversion window.The barrier effect of the SiO_2 shell effectively prevents the reduction of CuO species,which broadens temperature window of CO total conversion and enhances CO_2 selectivity above 155℃over the 1 CeO_2/CuO@SiO_2 catalyst in comparison with the CuO-CeO_2 and CeO_2-CuO catalysts.     

Novel promoting effects of cerium on the activities of NO_x reduction by NH_3 over TiO_2-SiO_2-WO_3 monolith catalysts

A series of catalysts were prepared by doping different loadings of CeO2 over TiO2-SiO2-WO3 and used for the selective catalytic reduction of NOx by NH3. The experimental results showed that the selective catalytic reduction（SCR） performance and SO2-resistant ability of TiO2-SiO2-WO3 were greatly enhanced by the introduction of cerium. The catalyst containing 10% CeO2 showed the highest NO conversion in a wide temperature range and good N2 selectivity with broad operation temperature window at the gas hourly space velocity（GHSV） of 30000 h–1, which was a very promising catalyst for NOx abatement from diesel engine exhaust. The catalysts were characterized by X-ray diffraction（XRD）, scanning electron microscopy with energy dispersive X-ray spectroscopy（SEM-EDS）, N2 adsorption-desorption（BET） and X-ray photoelectron spectroscopy（XPS）. The characterization results showed that the bigger pore radius, higher surface atomic concentration and dispersion of Ce and the abundant adsorbed oxygen on the surface of catalyst contributed to the best NH3-SCR performance of CeO2/TiO2-SiO2-WO3 catalyst containing 10% CeO2.     

Structure and oxygen storage capacity of Pd/Pr/CeOe-ZrO2 catalyst： effects of impregnated praseodymia

Praseodymium （Pr） was impregnated to CeO2-ZrO2 solid solution by an impregnation method. The as-obtained Pr modi- fied CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts. The structure and reducibility of the fresh and hydrother- really aged catalysts were characterized by X-ray diffraction （XRD）, Raman, X-ray photoelectron spectroscopy （XPS）, CO chemi- sorption and H2 temperature-programmed reduction （H2-TPR）. The oxygen storage capacity （OSC） was evaluated with CO serving as probe gas. Effects of impregnated Pr on the structure and oxygen storage capacity of catalysts were investigated. The results showed that the aged Pr-impregnated samples had much higher OSC and better reducibility than the unmodified ones. The scheme of structural evolutions of the catalysts with and without Pr was also established. Partial of the impregnated Pr diffused into the bulk of CeO2-ZrO2 during ageing, which inhibited the sintering, and increased the amount of oxygen vacancies in CeO2-ZrO2 support. Furthermore, those impregnated Pr species which covered on the surface of the support obstructed the strong metal-support interaction between Pd and Ce so as to reduce the encapsulation of Pd as well as the back spill-over of the oxygen during the catalytic process.     

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.     

Preparation,characterization and catalytic oxidation property of CeO2/Cu2+- attapulgite (ATP) nanocomposites

Cerium oxide (CeO₂) coated on copper modified attapulgite clay nanocomoposite (CeO₂/Cu²⁺-ATP) was prepared by homogeneous deposition method. The microstructures of the as-prepared CeO₂/Cu²⁺-ATP nanocomposites were characterized by X-ray diffraction (XRD), energy-dispersive spectrometer (EDS) and transmission electron microscopy (TEM). The results indicated that CeO₂ particles with average size of about 5 nm were loaded onto the Cu²⁺-ATP and were widely dispersed. Comparing the catalytic activity of ATP/CeO₂ and CeO₂/Cu²⁺-ATP, the catalytic activity was improved when a small quantity of Cu²⁺ was introduced. The loading amount of CeO₂ and reaction temperature had important effects on decolorization ratio of methyl orange (MO). When the loading amount and reaction temperature were 70% and 338 K, respectively, the decolorization ratio of MO reached over 99%, which showed excellent catalytic activity.     

Synergistic effects of CeO2/Cu2O on CO catalytic oxidation: Electronic interaction and oxygen defect

For CO catalytic oxidation, Cu and Ce species are of great importance, between which the synergistic effect is worth investigating. In this work, CeO₂/Cu₂O with Cu₂O {111} and {100} planes were comparatively explored on CO catalytic oxidation to reveal the effects of interfacial electronic interactions and oxygen defects. The activity result demonstrates that CeO₂/o-Cu₂O {111} has superior performance compared with CeO₂/c-Cu₂O {100}. Credit to the coordination unsaturated copper atoms (Cu_CUS) on o-Cu₂O {111} surface, the interfacial electronic interactions on CeO₂/o-Cu₂O {111} are more obvious than those on CeO₂/c-Cu₂O {100}, leading to richer oxygen defect generation, better redox and activation abilities of CO and O₂ reactants. Furthermore, the reaction mechanism of CeO₂/o-Cu₂O {111} on CO oxidation is revealed, i.e., CO and O₂ are adsorbed on the Cu_CUS on Cu₂O {111} and oxygen defect of CeO₂, respectively, and then synergistically promote the CO oxidation to CO₂. The work sheds light on the designing optimized ceria and copper-based catalysts and the mechanism of CO oxidation.     

Preparation and reaction mechanism of novel CexCoyCuz oxide composite catalysts towards oxidation of o-xylene

Ce_xCo_yCu_z oxide composite catalysts were prepared by using polyethylene glycol, citrate sol–gel method combined with PMMA template for the oxidation of o-xylene. The catalysts were characterized by the X-ray diffraction (XRD), H₂-temperature programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR), etc. The catalytic activity for o-xylene was investigated. The catalytic degradation pathway and mechanism of o-xylene were inferred. The results show that CeO₂ is mainly present on the surface of all catalysts. The surface area of Ce₂Co₁Cu₁ is up to 77.2 m²/g, and the average pore size is 10.62 nm. It exhibits redox and sufficient Ce⁴⁺ and Ce³⁺, and reactive oxygen species, and has maximum O–H and CO in the five catalyst samples. The catalytic activity of Ce₂Co₁Cu₁ is the best at low temperature, with the T₅₀ and T₉₀ values of 235 and 258 °C at a space velocity of 32000 h^?1, respectively. The o-xylene is oxidized to o-methyl benzaldehyde, and then further oxidized to o-methylbenzoic acid, and finally CO₂ and H₂O are formed.     

Effect of preparation method on MnOx-CeO2 catalysts for NO oxidation

The NO oxidation reaction was studied over MnO_x-CeO₂ catalysts prepared by co-precipitation, impregnation and mechanical mixing method, respectively. It was found that the co-precipitation was the most active and a 60% NO conversion was achieved at 250 °C. X-ray diffraction (XRD), Brumauer-Emmett (BET), H₂-temperature programmed reduction (H₂-TPR) and oxygen storage capacity (OSC) techniques were employed to characterize the physical and chemical properties of the catalysts. XRD results showed that amorphous MnO_x or Mn-O-Ce solid solution existed in co-precipitation and impregnation prepared sample, while crystalline MnO_x was found in mechanical mixing catalyst. A larger surface area was observed on co-precipitation prepared catalyst compared to those prepared by impregnation and mechanical mixing. The strong interaction between MnO_x and CeO₂ enhanced the reducibility of the oxides and increased the amount of Mn⁴⁺ and activated oxygen, which are favorable for NO oxidation to NO₂.     

Highly efficient K-doped Mn-Ce catalysts with strong K-Mn-Ce interaction for toluene oxidation

In this study,K_x-Mn-Ce catalysts prepared by sol-gel method were investigated for toluene oxidation.Compared with Mn-Ce,the catalytic performance of K_x-Mn-Ce was further improved.X-ray diffraction(XRD),high resolution transmission electron microscopy(HRTEM) and Raman analyses demonstrate that K ions enter the lattice of CeO₂ and disperse uniformly.The results of X-ray photoelectron spectroscopy(XPS),H₂-temperature programmed reduction(H₂-TPR...