Preparation of M/Ce1–xTixO2 (M=Pt,Rh, Ru) from sol-gel method and their catalytic oxidation activity for diesel soot

A series of Ce_1–xTi_xO₂ mixed oxide catalysts were synthesized by sol-gel method and then loading of noble metal (M = Pt, Rh, Ru) was used for soot oxidation. Ti-doped Ce_1–xTi_xO₂ catalysts (x is the molar ratio of Ti/(Ti + Ce) and ranges from 0.1 to 0.5) exhibit much better oxidation performance than CeO₂ catalyst, and the Ce_0.9Ti_0.1O₂ catalyst calcined at 500 °C has the best catalysis activity. Each noble metal (1 wt%) was supported on Ce_0.9Ti_0.1O₂ (M/C9T1) and the properties of the catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman, Brunauer–Emmett–Teller (BET) method, and H₂-temperature programmed reduction (H₂-TPR) results. Results show that the introduction of Ti into CeO₂ forming Ti-O-Ce structure enhances the catalytic activity and increases the number of oxygen vacancies at the catalyst surface. The noble metal is highly dispersed over Ce_0.9Ti_0.1O₂, and M/C9T1 catalysts present enhanced activity in comparison to Ce_0.9Ti_0.1O₂. It is found that noble metals can greatly increase the activity of the catalyst and the corresponding oxidation rate of soot can enhance the electron transfer capacity and oxygen adsorption capacity of the catalyst. A small amount of Ti doping in CeO₂ can significantly improve the activity of the catalyst, while a large amount of Ti reduces the performance of the catalyst because a large amount of Ti is enriched on the surface of the catalyst, which hinders the contact and reaction between the catalyst and the soot.     

Core-shell MnCeOx catalysts for NO oxidation and mild temperature diesel soot combustion

Environmental contamination such as soot particles and NO_x has aroused extensive attraction recently.However,the main challenge lies in the oxidation of soot at mild temperature with the assistance of NO_x.Here,a series of core-shell MnCeO_x catalysts were successfully synthesized by hydrothermal method and employed for low-temperature catalytic oxidation of soot in the presence of NO_x.X-ray diffraction(XRD),inductively coupled plasma-optical emission sp...     

Catalytic combustion of soot over Ru-doped mixed oxides catalysts

We employed modified substrates as outer heterogeneous catalysts to reduce the soot originating from the incomplete diesel combustion. Here, we proposed that ceria（CeO2）-based catalysts could lower the temperature at which soot combustion occurred from 610 oC to values included in the operation range of diesel exhausts（270–400 oC）. Here, we used the sol-gel method to synthesize catalysts based on mixed oxides（ZnO：CeO2） deposited on cordierite substrates, and modified by ruthenium nanoparticles. The presence of ZnO in these mixed oxides produced defects associated with oxygen vacancies, improving thermal stability, redox potential, sulfur resistance, and oxygen storage. We evaluated the morphological and structural properties of the material by X-ray diffraction（XRD）, Brumauer-emmett-teller method（BET）, temperature programmed reduction（H2-TPR）, scanning electron microscopy（SEM）, and transmission electron microscopy（TEM）. We investigated how the addition of Ru（0.5 wt.%） affected the catalytic activity of ZnO：CeO2 in terms of soot combustion. Thermogravimetric analysis（TG/DTA） revealed that presence of the catalyst decreased the soot combustion temperature by 250 oC, indicating that the oxygen species arose at low temperatures, which was the main reason for the high reactivity of the oxidation reactions. Comparative analysis of soot emission by diffuse reflectance spectroscopy（DRS） showed that the catalyst containing Ru on the mixed oxide-impregnated cordierite samples efficiently oxidized soot in a diesel stationary motor： soot emission decreased 80%.     

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...     

Surface reactive species on MnOx（0.4）-CeO2 catalysts towards soot oxidation assisted with pulse dielectric barrier discharge

MnOx(0.4)-CeO2 was investigated for soot oxidation assisted with a pulse dielectric barrier discharge(DBD).The catalysts were evaluated and characterized with TPO(temperature programmed oxidation),X-ray diffraction(XRD),Raman and X-ray photoelectron spectroscopy(XPS).The ignition temperature Ti for soot oxidation decreased from 240.8 to 216.4 oC with the increase of the pulse DBD frequencies from 50 to 400 Hz,lower than that of the case without pulse DBD present(253.4 oC).The results of XRD,Raman and XPS agreed well with the TPO activities of MnOx(0.4)-CeO2 towards soot oxidation.More solid solution of ceria and manganese,and surface reactive species including O2–,O– and Mn4+ were responsible for the enhancement of soot oxidation due to pulse DBD injection in the present study.For solid solution favors to the activation and transformation of those species,which are believed to be involved in the soot oxidation in a hybrid catalysis-plasma.     

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.     

Structure and catalytic property of CeO2-ZrO2-Fe2O3 mixed oxide catalysts for diesel soot combustion： Effect of preparation method

A series of Ce0.5Fe0.30Zr0.20O2 catalysts were prepared by different methods(co-precipitations method, citric acid sol-gel method, impregnation method, physical mixed method, and hydrothermal method) and characterized by X-ray diffraction(XRD), Raman spectroscopy, Brunauer-Emmett-Teller(BET) and H2-TPR measurements. Potential of the catalysts in the soot oxidation was evaluated in a temperature-programmed oxidation(TPO) apparatus. The results showed that all the Fe3+ and Zr4+ were incorporated into ceria lattice to form a pure Ce-Fe-Zr-O solid solution for the co-precipitation sample, but two kinds of Fe phases existed in the Ce-Fe-Zr-O catalysts prepared by other methods: Fe3+ incorporated into CeO2 lattice and dispersed Fe2O3 clusters. The free Fe2O3 clusters could improve the activity of catalysts for soot oxidation comparing with the pure Ce-Fe-Zr-O solid solution owing to the synergetic effect between free Fe2O3 and surface oxygen vacancies. In addition, the activity of catalysts strongly relied on the surface reducibility of free Fe2O3 particles. Holding both abundant free Fe2O3 particles and high oxygen vacancy concentration, the hydrothermal Ce0.5Fe0.3Zr0.2O2 catalyst presented the lowest Ti(251 °C, ignition temperature of soot oxidation) and Tm(310 °C, maximum oxidation rate temperature) for soot combustion(with tight-contact between soot and catalysts) among the five samples. Even after aging at 800 °C for 10 h, the Ti and Tm were still relatively low, at 273 and 361 °C, respectively, indicating high catalytic stability.     

Preparation and characterization of Ce-Fe-Zr-O(x)/MgO complex oxides for selective oxidation of methane to synthesize gas

A series of Ce-Fe-Zr-O(x)/MgO (x denotes the mass fraction of Ce-Fe-Zr-O, x=10%, 15%, 20%, 25%, 30%) complex oxide oxygen carriers for selective oxidation of methane to synthesis gas were prepared by the co-precipitation method. The catalysts were characterized by means of X-ray diffraction (XRD) and H₂-TPR. The XRD measurements showed that MgFeO₄ particles were formed and Fe₂O₃ particles well dispersed on the oxygen carriers. The reactions between methane diluted by argon (10% CH₄) and oxygen carriers were investigated. Suitable content of CeO₂/Fe₂O₃/ZrO₂ mixed oxides could promote the reaction between methane and oxygen carriers. There are mainly two kinds of oxygen of carriers: surface lattice oxygen which had higher activity but lower selectivity, and bulk lattice oxygen which had lower activity but higher selectivity. Among all the catalysts, Ce-Fe-Zr-O(20%)/MgO exhibited the best catalytic performance. The conversion of the methane was above 56%, and the selectivity of the H₂ and CO were both above 93%, the ratio of H₂/CO was stable and approached to 2 for a long time.     

Promotional effects of cerium doping and NOx on the catalytic soot combustion over MnMgAIO hydrotalcite-based mixed oxides

A series of MnMgA10 samples with different amounts of Ce doping were facilely prepared using coprecipitation method and their catalytic soot combustion activity was evaluated by temperature programmed oxidation reaction （TPO）. The methods of X-ray diffraction （XRD）, Brumauer-Emmett-Teller （BET）, H2-TPR, NO-TPO and in situ 1R were used to characterize the physio- chemical properties of these samples. Dopant Ce improved the soot combustion performance of MnMgA10 catalyst due to the en- hanced redox ability. Introduction of NOx led to the further increase of catalytic soot oxidation activity on these samples. Over Ce-containing samples, the catalytic activity was slightly decreased as the amount of dopant Ce increased in 02. Diftbrently, in NO＋O2, a certain amount of dopant Ce was much more favorable and excess amount of Ce resulted in a sharp drop of the catalytic soot combustion activity. Both NO： and nitrates were found to have great contributions to the effects of NOx on the soot combustion activity of Ce-doped catalysts. More NO2 was generated as dopant Ce increased. When appropriate amount of Ce was introduced, the as-formed NO2 was stored as bridging bidentate nitrate on Mn-Ce site, which was confirmed to have higher reactivity with soot than nitrite or monodentate nitrate on Mn and/or Ce sites. Overall, Mno.sMg2.sCeo.lAlo.90 was considered as the most potential catalyst for soot combustion.     

Active manganese oxide on MnOx–CeO2 catalysts for low-temperature NO oxidation: Characterization and kinetics study

MnO_x–CeO₂ catalysts were synthesized to investigate the active sites for NO oxidation by varying the calcination temperature. XRD and TEM results showed that cubic CeO₂ and amorphous MnO_x existed in MnO_x–CeO₂ catalysts. High temperature calcination caused the sintering of amorphous MnO_x and transforming to bulk crystalline Mn₂O₃. H₂-TPR and XPS results suggested the valence of Mn in MnO_x–CeO₂ was higher than pure MnO_x, and decreased with the increasing calcination temperature. The turnover frequency (TOF) was calculated based on the initial reducibility according to H₂-TPR quantitation and kinetic study. The TOF results indicated that the initial reducibility of amorphous MnO_x with high valence manganese ions was equivalent to the active sites for NO oxidation. It can be inferred that the amorphous MnO_x plays a key role in low-temperature NO oxidation.     

Active oxygen species and oxidation mechanism over Ce-doped LaMn_(0.8)Ni_(0.2)O_3/hierarchical ZSM-5 in pentanal oxidation

Hierarchical ZSM-5(HZ) molecular sieves based on fly ash were synthesized using a method combining water heat treatment with step-by-step calcination.The coupling catalysts between La_(1-x)Ce_xMn_(0.8)-Ni_(0.2)O_3(x ≤ 0.5) perovskites and HZ were prepared through the impregnation method,which were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),N_2 adsorption,X-ray photoelectron spectroscopy(XPS),NH_3-temperature programmed desoprtion(NH_3-TPD),H_2-temperature programmed reduction(H_2-TPR) and O_2-TPD techniques and investigated regarding pentanal oxidation at 120-390℃ to explore the effects of Ce doping on the catalytic activity and the active oxygen species of the coupling catalysts,meanwhile,the reaction mechanism and pathway of pentanal oxidation were also studied.The results reveal that Ce substitution at La sites can change the electronic interactions between all the elements and promote the electronic transfer among La,Ce,Ni,Mn and HZ,influencing directly the physicochemical characteristics of the catalysts.Moreover,the amount and transfer ability of surface adsorbed oxygen(O_2~-and O~-)regarded as the reactive oxygen species and the low temperature reducibility are the main influence factors in pentanal oxidation.Additionally,La_(0.8)Ce_(0.2)Mn_(0.8)Ni_(0.2)O_3/HZ exhibits the best catalytic activity and deep oxidation capacity as well as a better water resistance due to its larger amount of surface adsorbed oxygen species and higher low temperature reducibility.What's more,appropriate Ce substitution can significantly enhance the amount of O_2~-ions,which can distinctly enhance the catalytic activity of the catalyst,and moderate acid strength and appropriate acid amount can also facilitate the improvement of the pentanal oxidation activity.It is found that there is a synergic catalytic effect between surface acidity and redox ability of the catalyst.According to the in situ DRIFTS and GC/MS analyses,pentanal can be oxidized gradually to CO_2 and H_2 O by the surface oxygen species with the form of adsorption in air following the Langmuir-Hinshelwood(L-H) reaction mechanism.Two reaction pathways for the pentanal oxidation process are proposed,and the conversion of the formates to carbonates may be one of the main rate-determining steps.     

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.     

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.     

Promotion effect of niobium on ceria catalyst for selective catalytic reduction of NO with NH3

The CeO₂, Ce–Nb–O_x and Nb₂O₅ catalysts were synthesized by citric acid method and the promotion effect of Nb on ceria for selective catalytic reduction (SCR) of NO with NH₃ was investigated. The catalytic activity measurements indicate that the mixed oxide Ce–Nb–O_x presents a higher SCR activity than the single oxide CeO₂ or Nb₂O₅ catalyst. In addition, the Ce–Nb–O_x catalyst shows high resistance towards H₂O and SO₂ at 280 °C. The Raman, X-ray photoelectron spectra and temperature programmed reduction with H₂ results indicate that the incorporation of Nb provides abundant oxygen vacancies for capturing more surface adsorbed oxygen, which provides a superior redox capability and accelerates the renewal of active sites. Furthermore, the Fourier transform infrared spectra and temperature programmed desorption of NH₃ results suggest that niobium pentoxide shows high surface acidity, which is partly retained in the Ce–Nb–O_x catalyst possessing a high content of Lewis and Brønsted acid sites. Therefore, the incorporation of Nb improves both the redox and acidic capacities of Ce–Nb–O_x catalyst for the SCR reaction. Here, the redox behavior is primarily taken on Ce and the acidity is well improved by Nb, so the synergistic effect should exist between Ce and Nb. In terms of the reaction mechanism, in situ DRIFT experiments suggest that both NH₃ on Lewis acid sites and NH₄⁺ on Brønsted acid sites can react with NO species, and adsorbed NO and NO₂ species can both be reduced by NH₃. In the SCR process, O₂ primarily acts as the accelerant to improve the redox and acid cycles and plays an important role. This work proves that the combination of redox and acidic properties of different constituents can be feasible for catalyst design to obtain a superior SCR performance.     

Effects of loading transition metal(Mn,Cr,Fe,Cu) oxides on oxygen storage/release properties of CeO_2-ZrO_2 solid solution

Cerium zirconium-based(CZ) oxygen storage materials(OSMs) play a crucial role in three-way catalysts(TWCs),while CZ needs to be modified to satisfy more rigorous emission standard.In this study,transition metal(TMs=Mn,Cr,Fe,Cu) oxides modified CZ were prepared by incipient wetness impregnation method to improve the oxygen storage capacity of CZ-based materials.To clearly illustrate the influence of TM oxides,N_2 adsorption-desorption,X-ray diffraction(XRD),oxygen storage capacity(OSC),temperature programmed reduction by H_2(H_2-TPR) and X-ray photoelectron spectroscopy(XPS) were used to characterize the physical and chemical properties of samples.It is found that,all modified CZ have higher OSC,lower reduction temperatures than those of pristine CZ.Interaction between TMOs and CZ take precedence over specific surface to influence OSC.Notably,FeO_x/CZ has the highest OSC,which is about 1.9 times that of CZ and it could be attributed to synergistic effect between FeO_x and CZ;CuO_x/CZ has the lowest reduction temperature which is 168℃lower than that of CZ,and it can be explained by hydrogen spillover effect.     

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.     

In-situ generation of platinum nanoparticles on LaCoO3 matrix for soot oxidation

The LaCo_0.94Pt_0.06O₃ catalyst is reduced under 5% H₂/Ar at different temperatures to get Pt/LaCoO₃ with high catalytic activity for soot oxidation. Transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer–Emmett–Teller method (BET), X-ray photoelectron spectroscopy (XPS), H₂-temperature programmed reduction (H₂-TPR), O₂-temperature programmed desorption (O₂-TPD) and thermogravimetric analysis (TGA) were used to study the physicochemical properties of the catalyst. SEM and TEM results indicate that Pt nanoparticles (<10 nm) are grown homogeneously on the surface of the LaCoO₃ matrix after in-situ reduction. XRD shows that the reduced catalyst has a high symmetrical structure. TGA results indicate that all reduced catalysts exhibit an excellent activity, especially the catalyst reduced at 350 °C (T₁₀ = 338 °C, T₅₀ = 393 °C, T₉₀ = 427 °C). And perovskite is the primary active component. According to XPS study, the high symmetrical structure benefits the mobility of oxygen vacancy, and Pt nanoparticles induce the oxygen vacancy to move to its adjacent situation, resulting in more adsorbed oxygen on the surface of the reduced catalyst and increasing the activity. The possible reaction principle is also proposed.     

Promotional effects of samarium on Co3O4 spinel for CO and CH4 oxidation

A series of Co3O4 spinel catalysts modified by Sm were prepared by co-precipitation method and tested for CH4 and CO oxidation.The addition of a small amount of Sm into Co3O4 led to an improvement in the catalytic activity for both reactions.Co0.98Sm0.02 and Co0.95Sm0.05,the two samples with Co/Sm molar ratio of 0.98/0.02 and 0.95/0.05 in sequence,showed the similar and the highest activity for CH4 oxidation,with CH4 complete conversion at 450 oC.In contrast,Co0.90Sm0.10 was the most active sample for CO oxidation,with CO complete conversion at 120 oC.The catalysts were characterized by techniques of N2 adsortion-desorption with Brunauer-Emmett-Teller technique(N2-BET),X-ray powder diffraction(XRD),thermal gravity analysis-differential scanning calorimetry(TGA-DSC),H2 temperature programmed reduction(H2-TPR) and X-ray photoelectron spectroscopy analysis(XPS).Compared with pure Co3O4,for Co1–x Smx catalysts with 0.02≤x≤0.10,the addition of a small amount of Sm resulted in the formation of spinel Co3O4 and amorphous SmCoO3,hence increasing the number of Co3+ and the active surface oxygen species,which was responsible for the improvement of the activity.Co0.95Sm0.05 catalyst showed not only high thermal stability and activity but also good reaction durability in the presence of 5% water vapor for CH4 oxidation.     

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.