Catalytic performance of Zr-doped CuO-CeO_2 oxides for CO selective oxidation in H_2-rich stream

Zr-doped CuO-CeO_2 catalysts for CO selective oxidation were designed and prepared by the hydrothermal method and coprecipitation. The experimental samples were characterized by means of N_2 adsorption-desorption isotherms, powder X-ray diffraction, temperature-programmed reduction and Xray photoelectron spectroscopy. It is observed that the catalyst prepared by hydrothermal method exhibits larger specific surface area, smaller crystalline size and higher dispersion of active components compared with those of the catalyst obtained by coprecipitation. Meanwhile, redox properties of copper oxide are improved significantly and highly dispersed copper species providing CO oxidation sites are present on the surface. Furthermore, adsorptive centers of CO and active oxygen species increase on the copper-ceria interfaces. The Zr-doped CuO-CeO_2 catalyst prepared by hydrothermal method possesses superior catalytic activity and selectivity for selective oxidation of CO at low temperature compared with those of the sample prepared by coprecipitation. The temperature corresponding to 50% CO conversion is only 73 ℃ and the temperature span of total CO conversion is expanded from 120 to 160 ℃.     

Synthesis of La_xK_(1–x)CoO_3 nanorod and their catalytic performances for CO oxidation

A series of Lax K1–x CoO3 nanorod oxides with perovskite structure were synthesized by sol-gel method using polyvinyl alcohol(PVA) as additive.These perovskite-type complex oxide catalysts were characterized by the techniques of X-ray diffraction(XRD),infrared(IR),Brumauer-Emmett-Teller(BET) and scanning electron microscopy(SEM).And the results showed that nanorods of La1–x Kx CoO3 perovskite-type complex oxides were fabricated by sol-gel method when the mass concentration of PVA was 4% and the calcined temperature kept at 700 ℃ for 4 h.The catalytic results of CO oxidation showed that the Lax K1–x CoO3 catalysts had high activity.LaCoO3 nanorods exposed more {110} plane than LaCoO3 nanoparticles,which was beneficial to the catalytic oxidation of CO.LaCoO3 nanorods had the best catalytic performance for the oxidation of CO.At 200 oC,the CO conversion could reach 100%.     

Lanthanum-doped Cu-Mn composite oxide catalysts for catalytic oxidation of toluene

CuMn mixed oxides catalysts doped with La were prepared following a co-precipitation method and used for the catalytic oxidation of toluene. Catalysts properties of the catalysts were investigated by X-ray diffraction, N_2 adsorption/desorption,scanning electron microscopy, H_2-temperature-programmed reduction(H_2-TPR), O_2-temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy techniques. Characterization data reveal that the phase change and decrease in crystallinity of the La-doped catalysts increase the number of oxygen vacancies. Improvements in reducibility and an increase in the amount of chemisorbed oxygen of the La-doped catalysts were also verified by H_2-TPR and O_2-TPD. The activity of the CuMn mixed oxides catalysts is significantly improved by the addition of a nominal amount of La. The CuMn/La-4 mol% catalyst exhibits the best catalytic activity, with a 90%conversion temperature of 255 ℃,attributed to a high Mn~(3+)ratio, superficial chemisorbed oxygen,and high surface area. This study indicates La to be a promising dopant for Cu-Mn catalysts toward toluene oxidation.     

Synthesis and catalytic performance of macroporous La_(1-x)Ce_xCoO_3 perovskite oxide catalysts with high oxygen mobility for catalytic combustion of soot

The disordered macroporous-mesoporous La_(1-x)Ce_xCoO_3 catalysts were prepared by complexcombustion method with ethylene glycol as complexing agent at relatively low calcination temperature.The samples were characterized by means of X-ray diffraction,N2 adsorption-ndash;desorption,Xray photoelectron spectroscopy,transmission electron microscopy,hydrogen temperature-programmed reduction and soot temperature-programmed reduction,and so on.The results show that the use of complexing agent and relatively low calcination temperature increase the specific surface area of the catalyst and have abundant pore structure.The Ce ions introduced into lattice of LaCoO_3 mainly exist in the form of tetravalent.At the same time,Ce ions enhance the redox performance of the catalyst and the mobility of active oxygen species,which enhances the catalytic activity of the catalyst for soot combustion.The results of activity test show that La_(0.9)Ce_(0.1)CoO_3 catalyst exhibits the highest activity in the absence of NO and NO_2,and its T_(10),T_(50) and T_(90) are 371,444,and 497℃,respectively.At the same time,a possible reaction mechanism is proposed in this study based on the turnover frequency(TOF) calculated by isothermal anaerobic titrations,XPS and XRD results.     

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.     

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.     

Solution-Phase Synthesis and Characterization of Perovskite LaCoO3 Nanocrystals via A Co-Precipitation Route

A facile co-precipitation route for the synthesis of well-dispersed LaCoO3 nanocrystals was developed. The asprepared products were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, energy dispersive X-ray spectrometer （EDX）, and laser Raman spectroscopy （LRS）. The resuks showed that modulating the growth parameters, such as the addition of surfactants as well as the adding manner of the precipitator had a significant effect on the overall shape and size of the obtained nanocrystals. The nanorods with the diameter of 20 nm and spherical LaCoO3 nanocrystals with the size of about 25 nm could be obtained at a relatively low calcining temperature of 600℃. Furthermore, the Raman properties of LaCoO3 products obtained at different calcining temperatures were investigated.     

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.     

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.     

Effect of tourmaline additive on the crystal growth and activity of LaCoO3 for catalytic combustion of methane

LaCoO3/tourmaline was prepared as catalysts on the methane catalytic combustion. As additive tourmaline, its effect on crystal growth and catalytic activity of LaCoO3, were investigated via X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), H2-temperature programmed reduction(H2-TPR) and catalyst evaluation techniques. SEM and TEM indicated that the spontaneous polarizability of tourmaline made LaCoO3 particles grow dispersedly on tourmaline, alleviated the agglomeration and exposed more reactive sites. It was a main influence leading to the improvement of catalysts activity, exposed via catalyst evaluation device. Among the different additive proportion of compound samples, the 2% tourmaline added LaCoO3 showed an obvious enhancement activity compared to non-tourmaline sample—the light-off temperature was 454 °C and CH4 reached the full conversion at 563 °C.     

Catalytic wet oxidation of N,N-dimethyl formamide over ruthenium supported on CeO2 and Ce0.7Zr0.3O2 catalysts

A series of Ru supported on CeO₂ and Ce_0.7Zr_0.3O₂(CeZrO) was prepared by incipient-wet impregnation method and investigated in the catalytic wet oxidation of N,N-dimethyl formamide (DMF) in batch reactor. The physicochemical property of the catalysts was characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), H₂ temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG). Compared with 3%Ru/CeO₂, 3%Ru/Ce_0.7Zr_0.3O₂ catalyst exhibits much higher performance for DMF degradation due to the promotion of Ru dispersion and the transfer of active oxygen, and 99% DMF conversion and 97% COD elimination are obtained at 453 K, 2.5 MPa oxygen pressure after 5 h. The reaction mechanism of DMF degradation was suggested. The carbonaceous species deposition and oxidation of Ru can be responsible for catalyst deactivation. And the catalyst activity can be recovered by air calcination and H₂ reduction.     

Pseudo core-shell LaCoO_3@MgO perovskite oxides for high performance methane catalytic oxidation

Magnesia modified LaCoO_3 was prepared by a facile one-step sol-gel method and used for removal of dilute methane.Compared with the conventional doping technique,the obtained LaCoO_3@MgO-x exhibits pseudo core-shell structure and shows superior catalytic activity.The methane conversion exceeds90% at 532℃ on LaCoO_3@MgO-0.1,while only 60% of methane is conversed using the doped perovskite LaCo_(0.9)Mg_(0.1)O_3.The high catalytic performance of LaCoO_3@MgO-0.1 is mainly attributed to the adjustment of surface acid-base properties by the MgO shell structure.According to density functional theory(DFT) calculation,the methane is more likely to be adsorbed and cracked on LaCoO_3@MgO-0.1.The in situ DRIFTS shows that CH_3-O-CH_3 intermediate specie is formed.The pseudo core-shell structure also enhances the stability and the LaCoO_3@MgO-0.1 maintains high activity after working for 100 h.The above results demonstrate that surface modification by magnesia is an effective strategy for improving LaCoO_3 catalytic performance.     

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.     

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.     

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.     

CO oxidation and 4-nitrophenol reduction over ceria-promoted platinum nanoparticles impregnated with ZSM-5 zeolite

Active new ceria-promoted platinum supported on ZSM-5 catalysts were prepared and characterized by X-ray diffraction (XRD), Fourier transform infrared spectra (FTIR), transform electron microscopy (TEM), temperature programmed desorption (TPD), and FTIR of CO adsorption. The samples were prepared by the incipient wetness impregnation method and calcined at 500 °C. The XRD patterns and FTIR spectra prove that the zeolite framework is kept unaltered after metal loadings. TEM images prove the presence of Pt nanoparticles with particle size starting from 14 to 27 nm. The FTIR data suggest the formation of Pt–O–Ce linkage. In-situ FTIR of CO adsorption over reduced samples proves the presence of Pt⁰ only, and no Ptⁿ⁺–CO species are detected. The prepared catalysts were tested in both oxidation reaction (CO oxidation) in the gas phase and in reduction reaction (4-nitrophenol reduction) in the aqueous medium. Firstly, CO oxidation by O₂ results in the formation of a CO₂ peak at 2347 cm^?1 as the only CO oxidation product in the studied frequency range. The intensity of the CO₂ peak increases after the addition of Ce, and it is 4 times higher in Pt₁Ce_0.5ZSM-5 than that in the Ce-free sample. According to the FTIR data and previous reports, the increase in the catalytic activity may be due to the formation of Pt–O–Ce linkage. Secondly, Ce-promoted Pt₁ZSM5 also exhibits enhanced catalytic activity towards the reduction of 4-nitrophenol to 4-aminophenol by NaBH₄ in the aqueous medium. The first-order rate constant of the reduction increases ≈13 times after incorporating equal ratios of Pt and Ce (Pt₁Ce₁ZSM-5), and the activation energy (E_a) decreases to 40% of that in the reaction over Pt₁ZSM-5.     

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.     

CO oxidation over CuO catalysts supported on CeO2-ZrO2 prepared by microwave-assisted co-precipitation： The influence of CuO content

CeO2-ZrO2 mixed oxide(Ce0.6Zr0.4O2) prepared by microwave-assisted heating co-precipitation was used as a support to prepare a series of CuO/Ce0.6Zr0.4O2 catalysts with various CuO contents(0 wt.%–15 wt.%) via the method of incipient-wetness impregnation.The obtained CuO/Ce0.6Zr0.4O2 samples were characterized by N2 adsorption,XRD,Raman,TEM and H2-TPR technologies,and their catalytic activities for CO oxidation were investigated.The results showed that the activity of CuO/Ce0.6Zr0.4O2 catalyst was strongly influenced by the content of CuO,and the catalyst with 10 wt.% CuO exhibited the best catalytic activity in CO oxidation,which could be attributed to the high dispersion and reducibility of CuO,and high oxygen vacancy concentration in the catalyst.     

Effects of calcium substitute in LaMnO3 perovskites for NO catalytic oxidation

La1-x Cax MnO3 (x=0-0.3) perovskite-type oxides were synthesized by citrate sol-gel method. The physical and chemical properties were characterized by X-ray diffraction (XRD), Brumauer-Emmett-Teller method (BET), X-ray photoelectron spectroscopy (XPS), NO+O2 -TPD (temperature-programmed desorption), activated oxygen evaluation and H2 -TPR (temperature-programmed reduction) technologies. The results showed that NO catalytic oxidation activity was significantly improved by Ca substitution, especially for lower temperature activity. The La0.9 Ca0.1 MnO 3 sample showed the maximum conversion of 82% at 300 oC. The monodentate nitrates played a crucial role for the formation of NO2 . The reducibility of Mn 4+ ions and reactivity of activated oxygen were favorable for the catalytic performances of NO oxidation.