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.     

Luminescence tuning of Ce~(3+),Pr~(3+) activated(Y,Gd)AGG system by band gap engineering and energy transfer

Tuning of phosphor luminescence properties,including the emission energy/intensity and thermal stability,is an important way to develop superior luminescent materials for diverse applications.In this work,we discuss the effect of band gap engineering and energy transfer on the luminescence properties of Ce~(3+)or Pr~(3+) doped(Y,Gd)AGG systems,and analyze the underlying reasons for their different phenomena.By using VUV-UV excitation spectra and constructing VRBE schemes,the changes of host band structure,5 d excited level energies and emission thermal stability of Ce~(3+)and Pr~(3+) with the incorporation of Gd~(3+)ions were studied.In addition,the energy transfer dynamics was also investigated in terms of the luminescence decay curves.This work demonstrates a way to tune phosphor luminescence properties by combining band gap engineering and energy transfer tailoring and provides an inspiring discussion on the different results of Ce~(3+)doping on the Ce~(3+)and Pr~(3+)emissions.     

贵金属掺杂复合稀土氧化物的TPR研究

采用爆炸法合成系列钙钛矿结构复合氧化物La(RhMn)O3。利用程序升温还原法(H2-TPR)测试贵金属(Rh)掺杂复合稀土氧化物(LaM-nO3)的催化特性。结果表明,掺杂Rh后,低温还原峰峰温逐渐降低,钙钛矿的氧化性质发生了变化,氧缺陷和易移动的晶格氧增多。当掺杂少量Rh(0.2)后催化剂对H2的氧化温度明显降低,同时氧化能力明显提高。当Rh掺杂增加到一定量后,H2-TPR谱的高温还原峰面积和峰温又逐渐上升,钙钛矿结构趋于稳定。     

Effect of praseodymium additive on CeO_2(ZrO_2)/TiO_2 for selective catalytic reduction of NO by NH_3

A series of praseodymium added CeO_2(ZrO_2)/TiO_2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction(XRD), N_2-brumauer-emmett-teller(N_2-BET), NH_3-temperature programmed desorption(NH_3-TPD), H_2-temperature programmed reduction(H_2-TPR), PL spectra, Raman spectra, electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS), respectively. Influence of preparation method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO_2(ZrO_2)/TiO_2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO_2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO_2 forming the structure of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce~(3+) species, which was favourable for higher catalytic activity.     

Effect of PdO_x structure properties on catalytic performance of Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst for CO,HC and NO_x elimination

Pd/Ce_(0.67)Zr_(0.33)O_2 catalyst was pretreated in different atmosphere respectively, and characterized by CO chemical adsorption, XPS, HR-TEM, H_2-TPR, Raman, OSC and in situ DRIFTS to investigate the effect of the structure properties of PdO_x species on the catalytic performance for CO, HC and NO_x elimination. The results show that Pd/CZ catalyst pretreated in air atmosphere has higher oxidation activity of HC due to having high Pd dispersion and strong interaction between PdO_x and CZ support. Pd/CZ-H catalyst pretreated in reducing atmosphere exhibits better catalytic performance of NO_x elimination because of having relatively big Pd particle size, more Pd species in metallic state and higher concentration of oxygen vacancies. While for the Pd/CZ-RG catalyst pretreated in reactant atmosphere, strong adsorption of HC species on the surface of catalysts would lead to a part of active sites being covered, which inhibits HC and NO conversions.     

Effect of tungsten oxide on ceria nanorods to support copper species as CO oxidation catalysts

In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at% and 3.2 at%) was introduced to the ceria nanorods via a deposition-precipitation(DP) approach,and copper species of ca.10 at% were sequentially anchored onto the modified ceria support by a similar DP route.The aim of the study was to investigate the effect of the amount of tungsten oxide(0,0.4 at%,2.0 at%,and 3.2 at%) modifier on the copper-ceria catalysts for CO oxidation reaction and shed light on the structure-activity relationship.By the aids of multiple characterization techniques including N_2 adsorption,high-resolution transmission electron microscopy(HRTEM),powder X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),and temperature-programmed reduction by hydrogen(H_2-TPR) in combination with the catalytic performance for CO oxidation reaction,it is found that the copper-ceria samples maintain the crystal structure of the fluorite fcc CeO_2 phase with the same nanorod-like morphology with the introduction of tungsten oxide,while the textural properties(the surface area,pore volume and pore size) of ceria support and copper-ceria catalysts are changed,and the oxidation states of copper and tungsten are kept the same as Cu~(2+)and W~(6+)before and after the reaction,but the introduction of tungsten oxide(WO_3)significantly changes the metal-support interaction(transfer the CuO_x clusters to Cu-[O_x]-Ce species),which delivers to impair the catalytic activity of copper-ceria catalysts for CO oxidation reaction.     

H2BPMPBD和TOPO协同萃取Ln3+的研究

研究了1,4-双(1'-苯基-3'-甲基-5'-氧代吡唑-4'-基)丁二酮(H2BPMPBD,简为H2A)和三正辛基氧化膦(TOPO)的氯仿溶液从硝酸介质中对Ln3+的协同萃取.用斜率法确定了萃合物的组成为LaA·HA·TOPO,考察了萃取剂浓度和溶液酸度对萃取机理的影响,测定了半萃取pH1/2值和萃取反应平衡常数Ks.e,求得了反应的焓变和熵变.     

Steam reforming of ethanol over Ni/Ce0.7Pr0.3O2 catalyst

NiO/Ce0.7Pr0.3O2 catalysts were prepared by co-precipitation method and used for steam reforming of ethanol to produce hydrogen. The influence of nickel content and the doping of Pr on the catalytic performance were investigated. The catalysts were characterized by using temperature programmed reduction (TPR), X-ray diffraction (XRD) and thermal analysis techniques. 15 wt.%NiO/Ce0.7Pr0.3O2 catalyst was highly active and selective for steam reforming of ethanol to produce hydrogen. With the doping of Pr, the anti-carbon deposition property of the catalyst and the anti-sintering stability of metal nickel were effectively improved. The improvement of the anti-carbon deposition is attributed to generation of oxygen vacancies resulted from the Pr doping; while the improvement of anti sintering is ascribed to the intensified interaction between the nickel species and the support which is owing to the Pr-doping resulted incorporation of some nickel ions into ceria lattice.     

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.     

Cerium,manganese and cerium/manganese ceramic monolithic catalysts.Study of VOCs and PM removal

Ceramic supported cerium, manganese and cerium-manganese catalysts were prepared by direct impregnation of aqueous precursor, and characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Brunauer-Emmett-Teller method(BET), temperature programmed reduction(H_2-TPR), X-ray photoelectron spectroscopy(XPS) acidity measurements and electrical conductivity. The catalytic activity was evaluated for volatile organic compounds(VOC)(ethanol, methyl ethyl ketone and toluene) oxidation. Additionally, catalysts were tested in particulate matter(PM) combustion. The characterization results indicated that Ce was in the form of Ce~(4+) and Ce~(3+), and Mn existed in the form of Mn~(4+) and Mn~(3+) on the surface of the Mn/AC sample and in the form of Mn~(4+) in the Ce/Mn/AC monolith. VOC oxidation results revealed that the Ce/Mn/AC sample showed an excellent performance compared with ceramic supported CeO_2(Ce/AC) and MnO_x(Mn/AC) samples. The PM combustion was also higher on Ce/Mn/AC monoliths. The enhanced catalytic activity was mainly attributed to the Ce and Mn interaction which enhanced the acidity, conductivity and the reducibility of the oxides.     

The variation of microstructures,spectral characteristics and catalysis effects of Fe~(3+) and Zn~(2+) co-doped CeO_2 solid solutions

Fe~(3+)and Zn~(2+)ions were doped into the lattice of CeO_2 via the hydrothermal method.The micro structure and spectra features were analyzed systemically.XRD results show that the solid solubility of Fe~(3+)and Zn~(2+)ions in Ce_(1-x)(Fe_(0.5)Zn_(0.5))_xO_2 can be identified as x=0.16.The cell volumes are decreased by increasing the doped content.The TEM graphs prove that the grain size of the sample is about 10 nm,and the EDS result indicates that the doped contents are in accordance with that of the theory concentrations.Meanwhile,the doping also causes the increasing concentrations of the defects and oxygen vacancies which are supported by the XPS,Raman,UV and PL characterizations.The samples exhibit better catalytic activities for improving the hydrogen storage properties and the electrochemical kinetics of the ball milled Mg_2Ni based composites.Further,the catalysis effects are improved by increasing the doped contents,which can be ascribed to the increasing contents of the oxygen vacancies,defects,the special electron transition states and the nature of the doped ions in CeO_2-based solid solutions.     

H_3BO_3添加量对CaTiO_3∶Pr~(3+)余辉性能的影响

采用高温固相法合成CaTiO3∶Pr3+,并通过掺杂H3BO3改性。研究样品的发射光谱、发光亮度及余辉时间,探讨H3BO3添加量对CaTiO3∶Pr3+发光强度及余辉性能的影响。结果表明,所添加H3BO3的摩尔分数为15%时,CaTiO3∶Pr3+粉末具有最佳的余辉性能。     

Catalytic performance of a Pt-Rh/CeO_2-ZrO_2-La_2O_3-Nd_2O_3 three-way compress nature gas catalyst prepared by a modified double-solvent method

A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt~0 species and larger Ce~(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.     

Structure and oxygen storage capacity of Pd/Pr/CeO_2-ZrO_2 catalyst:effects of impregnated praseodymia

Praseodymium(Pr) was impregnated to CeO2-ZrO2 solid solution by an impregnation method.The as-obtained Pr modified CeO2-ZrO2 was impregnated with 1 wt.% Pd to prepare the catalysts.The structure and reducibility of the fresh and hydrothermally aged catalysts were characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),CO chemisorption 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.     

红色长余辉发光材料BaMg_2Si_2O_7∶Pr,Mn的制备及性质研究

采用高温固相法合成了红色长余辉材料BaMg2Si2O7∶Pr,Mn,利用X晶体衍射仪、扫描电镜、荧光光谱、热释光测量仪等对材料的性能进行了表征,结果分析证明BaMg2Si2O7∶Pr,Mn以Mn2+为发光中心,Pr3+为共激活离子,在紫外光的照射下能够得到由Mn2+的4T1(4G)→6A1(6S)跃迁产生的峰值在666nm发射峰,产生红光发射,撤离激发光源后,能够产生余辉,且余辉时间可以持续达40分钟以上,基质中存在着Pr3+→Mn2+的能量传递,能够增强其荧光发射峰强度并对余辉性能有一定促进作用。     

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.     

New insights into the role of vanadia species as active sites for selective catalytic reduction of NO with ammonia over VO_x/CeO_2 catalysts

A series of VO_x/CeO_2 catalysts we re synthesized via vanadia supported on ceria with different BET surface areas.The catalysts were employed to investigate the active sites for the selective catalytic reduction of NO with NH_3(NH3-SCR).The kinetic results show that VO_x/CeO_2 catalysts exhibit nearly constant apparent activation energies(E_a),indicating the same SCR reaction mechanism.The V-O-Ce bridging modes and oligomeric VO_x were identified and quantified by Raman,FT-IR and H_2-TPR.The amounts of the V-O-Ce bridging modes calculated by H_2-TPR are correlated to the NH_3-SCR intrinsic reaction rates.The turnover frequencies(TOFs) show a constant value at the same temperature,which were calculated based on the number of V-O-Ce bridging modes of VO_x/CeO_2 catalysts.Therefore,it can be concluded that the V-O-Ce bridging modes are the active sites of VO_x/CeO_2 catalysts for the NH3-SCR reaction.     

The effect of hydrogen peroxide on properties of Ce_(0.35)Zr_(0.55)La_(0.055)Pr_(0.045)O_2 oxides and the catalytic performance used on Pd supported three-way catalyst

In this study,two series of cerium zirconium mixed oxides Ce_(0.35)Zr_(0.55)La_(0.055)Pr_(0.045)O_2 were prepared under traditional co-precipitation and oxidation co-precipitation methods respectively. The physicochemical properties of the samples were compared under these two methods and assessed by XRD,Raman,BET,TEM,H_2 TPR,OSC,XPS and catalysts measurements. The formation of homogeneity phase structure can be facilitated by changing the precipitating properties of Ce3+ under oxidation coprecipitation method, which is helpful to enhance the homogeneity of Ce and Zr at atomic level.What's more, it is conducive to remove impurities Na~+ and Cl~-by oxidation co-precipitation with hydrogen peroxide. The catalysts activities are related to both the redox properties and the textural properties of mixed oxides. The Pd-only TWCs supported on the CZLP-H-F exhibits better catalytic performance and thermal stability with wider air/fuel ratio operation window, lower light-off and full conversion temperatures of C_3 H_8 and NO. The homogeneity of phase structure for cerium zirconium mixed oxide can be predicted and deduced from detecting the atomic distribution uniformity of its precursor. So this work not only provides insights into the mechanisms for phase segregation of cerium zirconium mixed oxide, but also provides a guidance to improve homogeneity of cerium zirconium mixed oxide by adding additives.     

Effect of template on catalytic performance of La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3 for ethanol steam reforming reaction

Perovskite-type oxides La_(0.7)Ce_(0.3)Ni_(0.7)Fe_(0.3)O_3(LCNF) were synthesized by polystyrene colloidal crystal templating(LCNF-CCT) and polystyrene polymer templating(LCNF-PS) through co-precipitation. The structure and physicochemical properties of the obtained oxides were investigated by scanning electron microscopy, X-ray diffraction, N_2 adsorption-desorption, Fourier transform infrared spectrometry, H_2 temperature-programmed reduction and H_2 temperature-programmed desorption, as well as X-ray photoelectron spectroscopy. The results show that the as-synthesized LCNF-CCT perovskite possesses large specific surface area and regular pore size distribution. In addition, the formation of additional oxygen vacancies on the surface favors the migration of lattice oxygen from the bulk phase to the surface and production of more metallic sites, thus improving the activity and resistance to carbon deposition of catalysts in ethanol steam reforming reaction.