Copper-ceria sheets catalysts: Effect of copper species on catalytic activity in CO oxidation reaction

Copper-ceria sheets catalysts with different loadings of copper(2 wt.%, 5 wt.% and 10 wt.%) supported on ceria nanosheets were synthesized via a depositioneprecipitation(DP) method. The prepared catalysts were systematically characterized with various structural and textural detections including X-ray diffraction(XRD), Raman spectra, transmission electron microscopy(TEM), X-ray absorption fine structure(XAFS), and temperature-programmed reduction by hydrogen(H_2-TPR), and tested for the CO oxidation reaction. Notably, the sample containing 5 wt.% of Cu exhibited the best catalytic performance as a result of the highest number of active CuO species on the catalyst surface. Further increase of copper content strongly affects the dispersion of copper and thus leads to the formation of less active bulk CuO phase, which was verified by XRD and H_2-TPR analysis. Moreover, on the basis of in-situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS) results, the surface Cu~+ species, which are derived from the reduction of Cu~(2+), are likely to play a crucial role in the catalyzing CO oxidation.Consequently, the superior catalytic performance of the copper-ceria sheets is mainly attributed to the highly dispersed CuO_x cluster rather than Cu-[O_x]-Ce structure, while the bulk CuO phase is adverse to the catalytic activity of CO oxidation.     

Effective removal of automobile exhausts over flower-like Ce1−xCuxO2 nanocatalysts exposed active {100} plane

This work elucidates the synthesis and characterization of copper ions incorporated ceria(Ce_(1-x)Cu_xO_2)nanocatalysts with 3 D flower-like and nanocrystalline morphology for the purification of automobile exhausts. XRD and Raman results confirm the presence of copper ions in ceria. The 3 D flower-like and nanocrystalline morphology exhibited by these catalysts were seen by FESEM images. HRTEM and SAED results confirm that(100) plane is dominantly presented in 3 D flower-like Ce_(1-x)Cu_xO_2 catalysts when compared to nanocrystalline morphology. The textural properties of synthesized catalysts was done with the help of N2 sorption study, which confirms that flower-like Ce_(1-x)Cu_xO_2 catalysts show high surface area and pore volume. The existence of Ce~(3+), Ce~(4+), Cu~+ and Cu~(2+) ions in the catalyst were examined by XPS and DR UV-Vis techniques. Oxygen storage capacity(OSC) of the catalysts was studied by H_2-TPR analysis. These characterization results elucidate the presence of dominant active sites(Ce~(3+), Ce~(4+), Cu~+and Cu~(2+)) and {100} plane in the flower-like morphology compared to nanocrystalline. The catalytic activity of synthesized Ce_(1-x)Cu_xO_2 catalysts was tested for removal of CO, HC_x and NO gases from automobile emission with respect to the copper content and morphology. The obtained results indicate that the presence of optimum amount of copper in ceria with flower-like morphology is essential for the removal of CO, HC_x and NO at low temperature via redox process, which is due to the presence of active sites on the dominant {100} plane.     

Effect of yttrium addition on water-gas shift reaction over CuO/CeO2 catalysts

This paper presented a study on the role of yttrium addition to CuO/CeO2 catalyst for water-gas shift reaction. A single-step co-precipitation method was used for preparation of a series of yttrium doped CuO/CeO2 catalysts with yttrium content in the range of 0-5wt.%. Properties of the obtained samples were characterized and analyzed by X-ray diffraction (XRD), Raman spectroscopy, H2-TPR, cyclic voltammetry (CV) and the BET method. The results revealed that catalytic activity was increased with the yttrium content at first, but then decreased with the further increase of yttrium content. Herein, CuO/CeO2 catalyst doped with 2wt.% of yttrium showed the highest catalytic activity (CO conversion reaches 93.4% at 250℃) and thermal stability for WGS reaction. The catalytic activity was correlated with the surface area, the area of peak y of H2-TPR profile (I.e., the reduction of surface copper oxide (crystalline forms) interacted with surface oxygen vacancies on ceria), and the area of peak C2 and A1 (Cu0→Cu2+ in cyclic voltammetry process), respectively. Besides, Raman spectra provided evidences for a synergistic Cu-Ovacancy interaction, and it was indicated that doping yttrium may facilitate the formation of oxygen vacancies on ceria.     

Structure and Catalytic Behavior of CuO-ZrO-CeO2 Mixed Oxides

The effect of doping CuO on the structure and properties of zirconia-ceria mixed oxide was studied. The results show that addition of CuO decreases the reduction temperature of ceria, and stabilizes the cubic structure of mixed oxides, and enhances catalytic activity of CuO-ZrO-CeO2 mixed oxides for CO oxidation. Increasing ceria content in the mixed oxides can enhance the catalytic activity, but some impurities such as sulfate make catalytic activity falling. There is little effect of calcination temperature on catalytic activities, implying that these catalysts are effective with good thermal stability.     

CuO／CeO2 Catalysts for Selective Oxidation of Carbon Monoxide in Excess Hydrogen

CuO/CeO2 catalysts were prepared by a coprecipitation method and tested for CO removal from reformed fuels via selective oxidation. The influence of the calcination temperature on the chemical compositions and catalytic performance of CuO/CeO2 catalysts were studied. It was found that CuO/CeO2 catalysts exhibit excellent CO oxidation activity and selectivity, and the complete removal of CO is attained when the catalysts are calcined at appropriate temperatures. XRD, TPR and XPS results indicate that CuO/CeO2 catalysts exhibit higher catalytic performance in CO selective oxidation due to the strong interaction between copper oxide and cerium dioxide, which promotes the dispersion and hydrogen reduction activity of copper.     

Preparation and characterization of Ce_(1-x)Pr_xO_2 supports and their catalytic activities

In this work, the addition of praseodymium(Pr) into ceria as a mixed oxide support in a form of Ce_(1-x)Pr_xO_2(x = 0.01,0.025, 0.050, 0.075 and 0.10) was prepared using a co-precipitation method. The structural and textural properties of the synthesized supports were characterized by X-ray diffraction(XRD), N_2 adsorption-desorption, Raman spectroscopy, H_2-temperature programmed reduction(H_2-TPR) and H_2-chemisorption. Upon addition of Pr, XRD patterns and Raman spectra indicated an enlargement of ceria unit cell and the characteristics Raman broad peak at 570 cm~(-1) which was attributed to the existence of oxygen vacancies in the ceria lattice. This indicated that some Ce~(4+) ions in ceria were replaced by larger Pr~(3+) cations. To evidence the incorporation of Pr~(3+) cations into ceria lattice,X-ray absorption near edge structure(XANES) was employed. The results showed that the oxidation states of Ce in mixed oxide supports were slightly lower than 4+ while those of Pr were still the same as a precursor salt. Therefore, the incorporation of Pr~(3+) into ceria lattice would lead to strain and unbalanced charge and result in oxygen vacancies. The reducibility of Ce_(1-x)Pr_xO_2 mixed oxide supports was investigated by H_2-TPR and temperature-resolved X-ray absorption spectroscopy experiment under reduction conditions. XANES spectra of Ce L_3 edges showed a lower surface reduction temperature(Ce~(4+)to Ce~(3+)) of Ce_(0.925)Pr_(0.075)O_2 than that of CeO_2 which agreed with H_2-TPR results. H_2-chemisorption indicated that Pr promoted the dispersion of the metal catalyst on the mixed oxide support and increased the adsorption site for CO. For WGS reaction, 1% Pd/mixed oxide support had higher WGS activity than 1%Pd/ceria. The increase of WGS activity was due to the increase of Pd dispersion on the support and the existence of oxygen vacancies produced from incorporation of Pr into the ceria lattice.     

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 ℃.     

Preparation and characterization of Cu-Ce-La mixed oxide as water-gas shift catalyst for fuel cells application

Cu-Ce-La mixed oxides were prepared by three precipitation methods （coprecipitation, homogeneous precipitation, and deposition precipitation） with variable precipitators and characterized using X-ray diffraction, BET, temperature-programmed reduction, and catalytic reaction for the water-gas shift. The Cu-Ce-La mixed oxide prepared by coprecipitation method with NaOH as precipitator presented the highest activity and thermal stability. Copper ion substituted quadrevalent ceria entered CeO2 （111） framework was in favor of activity and thermal stability of catalyst. The crystallinity of fresh catalysts increased with the reduction process. La^3＋ or Ce^4＋ substituted copper ion entered the CeO2 framework during reduction process. The coexistence of surface copper oxide （crystalline） and pure bulk crystalline copper oxide both contributed to the high activity and thermal stability of Cu-Ce-La mixes oxide catalyst.     

Ceria modified three-dimensionally ordered macro-porous Pt/TiO2 catalysts for water-gas shift reaction

Three-dimensionally ordered macro-porous(3DOM) TiO2 and ceria-modified 3DOM TiO2 supported platinum catalysts were pre-pared with template and impregnation methods, and the resultant samples were characterized by scanning electron microscopy(SEM), X-ray dif-fractometer(XRD), high-resolution transmission electron microscopy(HRTEM) and texture programmed reduction(TPR) techniques. The catalytic performances over the platinum-based catalysts were investigated for water-gas shift (WGS) reaction in a wide temperature range macro-porous catalyst, owing to the macro-porous structure favoring mass uansfer. Addition of ceria into 3DOM Pt/TiO2 led to improvement of catalytic activity. TPR and HRTEM results showed that the interaction existed between ceria and titanium oxide and addition of ceria promoted the reducibility of platinum oxide and TiO2 on the interface of platinum and TiO2 particles, which contributed to high activity of the ceria modi-fied catalysts. The results indicated that ceria-modified 3DOM Pt/TiO2 was a promising candidate of fuel cell oriented WGS catalyst.     

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.     

Catalytic oxidation of CO on mesoporous codoped ceria catalysts:Insights into correlation of physicochemical property and catalytic activity

Codoping approach is an appealing strategy to further improve the catalytic activity of Ce-based catalysts. In the present study,Mn and/or Cu doped ceria solid solutions MnxCuyCe_(1-x-y)O_2,Cu_xCe_(1-x)O_2,Mn_xCe_(1-x)O_2 and pure CeO_2 were prepared by CTAB-assisted hydrothermal method for CO oxidation.XRD, SEM, EDS, BET, Raman, H2-TPR, XPS and in situ DRIFTS techniques were carried out to study the physicochemical properties and to correlate them to the activity. The doped samples maintain the cubic fluorite structure of CeO_2 with high crystallinity and small crystallite size, forming Ce-based solid solutions. The obtained catalysts have large mesoporous structure with average pore size of 10-14 nm. The doped transition metal enhances the oxygen vacancies and improves reducibility of the solids. The synergistic interaction of Mn and Cu codoping induces mo re oxygen vacancies, pro moting the increase of surface adsorbed oxygen and the transfer of bulk oxygen of catalyst, thereby enhancing the catalytic activity for CO oxidation. Besides, the decomposition rate of the carbonate species which is derived from in situ DRIFTS for each catalyst can provide a measure to evaluate its catalytic activity of CO oxidation.     

LaO_x(OH)_y supported platinum catalysts for CO oxidation:Deactivation by formation of lanthanum carbonate

Platinum catalyst for CO oxidation has been studied for decades,due to its high activity and good stability.In this work,we prepared three different lantha num oxide or hydroxide supports(LaO_x(OH)_y),and deposited platinum(Pt) with 0.5 at% via an impregnation approach to synthesize Pt/LaO_x(OH)_y catalysts.However,we find that these catalysts perform a poor stability for the CO oxidation reaction.The fresh and used samples were comprehensively characterized by multiple techniques including power X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),transmission electron microscopy(TEM),temperature-programmed reduction by carbon monoxide(CO-TPR) and thermogravimetric analysis(TGA),to demonstrate that the oxidized platinum atoms or clusters,without any component of Pt-Pt metallic bond,are highly dispersed on the surface of LaO_x(OH)_y.Furthermore,the as-formed lanthanum carbonate(La₂O₂CO₃) during the exposure to ambient circumstances or in the reaction atmosphere of CO+O₂,severely impair the reactivity of Pt/LaO_x(OH)_y.On the basis of the obtained experimental results,we have drawn a conclusion that the oxidized P_tO_x atoms or PtxOy clusters are the active species for CO oxidation,while the formation of lanthanum carbonate is the origin of deactivation on reactivity.     

Influence of Additives Ceria and Lanthana on Performance of Pd／Al／Monolith Honeycomb Catalysts

The effects of ceria and lanthana additives on activity and thermal stabilization of the catalysts for CO oxidation were studied. The results show that the addition of CeO2 clearly improves the catalytic activity, which may derive from the synergic effect between CeO2 and PdO. The catalysts were characterized by means of temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS) measurements. The XPS results of a slight increase in metal oxidation state reflect that the charge transfers from metal to ceria and ceria is slightly reduced, which leads to a decrease of the Ce-O bond strength. Pd-Ce synergism affects the reduction behavior of the catalysts. The TPR results show that the CeO2 ad-dition lowers the reduction temperature of PdO, while palladium facilitates the reduction of the ceria. For PdO/La2O3/Al2O3/monolith honeycomb catalysts, the aging test measurements at 1050 ℃ and the XRD results show that the formation of LaAlO3 which neutralizes the surface alumina defects inhibits the sintering of alumina.     

Zirconia-Supported Copper Oxide—A Catalyst for Removal of Vehicular Exhaust Gas Pollutants

Copper oxide and zirconia-supported copper oxide catalysts were tested for their catalytic activity for carbon monoxide and propylene oxidation reactions. The synthesized catalyst was supported by wet impregnation on zirconia. The higher activity of zirconia-supported catalyst compared to unsupported catalyst may be attributed to homogeneous and higher dispersion on zirconia, ionic oxygen carrying capacity of zirconia. Catalyst 10%?CuO/ZrO2 showed a best conversion efficiency of 90% at a temperature as low as 265°C for CO oxidation. T50 and T100 for propylene oxidation on zirconia-supported copper oxide were 392 and 450°C, respectively.     

Effect of preparation method on the catalytic activity of Au/CeO2 for VOCs oxidation

The Au/CeO2 catalysts were synthesized by co-precipitation (CP), deposition-precipitation (DP) and metallic colloids deposition (MCD) method, and tested for oxidation of volatile organic compounds (VOCs). It was revealed that the Au/CeO2 catalyst prepared by DP method was the most efficient catalyst towards the total oxidation of toluene. The Au/CeO2 catalysts had obviously high catalytic activity, and the best results was obtained on 3 wt.% Au/CeO2 catalyst prepared by DP method. These catalysts were chara...     

Preparation and CO conversion activity of ceria nanotubes by carbon nanotubes templating method

Ceria nanotubes with high CO conversion activity by means of carbon nanotubes as removable templates in the simple liquid phase process were fabricated under moderate conditions. The pristine CNTs were first pretreated by refluxing in a 30% nitric acid solution at 140 ℃ for 24 h, then dispersed in an ethanolic Ce（NO3）3.6H2O solution with ultrasonic radiation at room temperature for 1 h. Under vigorous stirring, NaOH solution was added drop by drop into the above ethanolic solution until the pH value was 10. The product was collected and repeatedly washed with ethanol and on drying at 60 ℃, the CeO2/CNT composites were obtained. Then, the as-prepared composites were heated at 450 ℃ in an air atmosphere for 30 min to remove CNTs. The ceria nanotubes were characterized by X-Ray Diffraction （XRD）, Transmission Electron Microscopy （TEM）, and X-Ray Photoelectron Spectrum （XPS）. The results showed that the ceria nanotubes were polycrystalline face-centered cubic phase and were composed of lots of dense cefia nanoparficles. The diameter of cefia nanotubes was about 40-50 nm. Catalytic activity of the product for CO oxidation was carded out at the region of 30-300 ℃ in a U-shaped quartz reactor with feeding about 0.15 g of the catalyst, which was loaded on Al2O3 carder. The inlet gas composition was 1.0% CO and 28% O2 with N2 as balance, and the rate of flow was kept at 40 ml/min. The catalytic products were analyzed by gas chromatography. The as-repared CeO2 nanotubes showed higher CO oxidation activity, which indicated that the morphology of ceria products affected the catalytic performance. The ceria nanotubes supported on Al2O3 demonstrated that conversion temperature for CO oxidation to CO2 was lower than that for bulk catalysts.     

Effects of ZrO2 Content on Structure and Performance of Cu/CeO2-ZrO2 Catalysts for Water-Gas Shift Reaction

Water-gas shift(WGS)is a critical step in fuelprocessors for preli minary COclean-up and additionalhydrogen generation prior to the CO clean-up stage,which opened up new potential applications for WGScatalysts.Recently several formulations of noble-met-al…     

Zirconia modified monolithic macroporous Pt/CeO2/Al2O3 catalyst used for water-gas shift reaction

Monolithic macroporous Pt/CeO2/Al2O3 and zirconia modified Pt/CeO2/Al2O3 catalysts were prepared by using concentrated emulsions synthesis route. The catalytic performances over the platinum-based catalysts were investigated by water-gas shift (WGS) reaction in a wide temperature range (180-300 oC). The samples were characterized with thermogravimetry (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and temperature programmed reducti...     

Valence State of Active Copper in CuOx/CeO2 Catalysts for CO Oxidation

CuOx/CeO2 catalysts were prepared by adsorption-impregnation method, CO conversion was tested over the catalysts pretreated under different conditions for preferential CO oxidation in H2, and the catalysts were characterized with X-ray photoelectron spectroscopy and temperature programmed reduction. Experimental results show that there are two kinds of copper, which are Cu^＋ and Cu^2＋ in calcined CuOx/CeO2, Among them, the Cu^＋ is the key active component for CO oxidation. The main reason is as follows： CO is activated by copper for CO oxidation over CuOx/CeO2, while CO can not be activated by Cu^2＋. Only when Cu^2＋ is reduced to Cu ^＋ or Cu^0, the copper may be active for CO oxidation, moreover, the experimental results show that the reduction of Cu^2＋ does not lead to an increase of catalytic activity. So the active species is Cu^＋ in CuOx/CeO2 catalysts.     

Reverse water gas shift reaction over Co-precipitated Ni-CeO2 catalysts

The Ni-CeO2 catalysts with different Ni contents were prepared by a co-precipitation method and used for Reverse Water Gas Shift （RWGS） reaction. 2wt.%Ni-CeO2 showed excellent catalytic performance in terms of activity, selectivity, and stability for RWGS reaction. Characterizations of the catalyst samples were conducted by XRD and TPR. The results indicated that, in Ni-CeO2 catalysts, there were three kinds of nickel, nickel ions in ceria lattice, highly dispersed NiO and bulk NiO. Oxygen vacancies were formed in CeO2 lattice due to the incorporation of Ni^2＋ ions into ceria lattice. Oxygen vacancies formed in ceria lattice and highly dispersed Ni were key active components for RWGS, and bulk Ni was key active component for methanation of CO2.