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.     

Influence of preparation method on performance of Ni-CeO2 catalysts for reverse water-gas shift reaction

This study investigated 1 wt.% Ni-CeO₂ catalysts that were prepared using co-precipitation, deposition-precipitation, and impregnation methods for the reverse water-gas shift (RWGS) reaction. Characterizations of the catalyst samples were conducted by Brumauer-Emmett-Teller (BET), atomic absorption spectrophotometer (AAS), X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM) and temperature programmed reduction (TPR). The results showed that the Ni-CeO₂ catalyst prepared using the co-precipitation method exhibited the best catalytic performance. In the Ni-CeO₂ catalyst prepared using co-precipitation method, a combination of highly dispersed NiO and abundant oxygen vacancies was assumed to play a crucial role in determining the catalytic activity and selectivity of the RWGS reaction.     

Preparation and characterization of Ce_1-xNi_xO₂ as oxygen carrier for selective oxidation methane to syngas in absence of gaseous oxygen

A citric acid complex method was employed to prepare Ce/Ni mixed oxides with various Ce/Ni ratios useful for selective oxidation methane to syngas in the absence of gaseous oxygen,and the catalytic activity measurement was investigated in a fixed bed reactor at 800 oC.The prepared oxygen carriers were characterized by various characterization techniques such as TG-DSC,XRD and TPR.The results of TG-DSC indicated that the Ce1-xNixO2 precursor generated a stable phase after the heat-treatment at temperatures above 800 oC.The XRD characterization suggested that some Ce-Ni solid solution was formed when Ni2+ ions was incorporated into the lattice of CeO2,and it led to the generation of O-vacancy which could improve the oxygen mobility in the lattice of oxygen carriers.It was found that Ce0.8Ni0.2O2 gave the highest activity in the selective oxidation methane to syngas reaction,and the average methane conversion,CO and H2 selectivity reached to 82.31%,82.41% and 87.64%,respectively.The reason could be not only attributed to the fitting amount of NiO dispersed on the CeO2 surface and bulk but also to actual lattice oxygen amount increased in oxygen carrier.     

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.     

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.     

晶格氧部分氧化甲烷制合成气及其氧扩散行为研究

介绍了一种在熔融盐中利用金属氧化物的晶格氧部分氧化甲烷制合成气的新方法。以NiO为氧载体对其部分氧化甲烷的氧扩散行为进行了初步研究。利用XRD和GC等分析手段,在自行设计的氧扩散行为研究反应器中对熔融盐体系和产物气进行了分析研究。结果表明,在800℃的碳酸熔融盐中,CH4通过不含NiO氧载体的熔融盐层时H2、CO浓度仅为13.67%和20%,而通过含NiO氧载体的熔融盐层时H2、CO浓度明显增至45.9%和24.5%;实验表明NiO能够提供出自身晶格氧把CH4部分氧化成n(H2)/n(CO)接近理论值2的合成气;NiO在熔融碳酸盐体系中虽有少量溶解,但主要不以离子化形式扩散氧,而是CH4与NiO分子间发生气固反应占主导,在这一过程中NiO分子中晶格氧是甲烷部分氧化的活性氧物种。     

Calculation of activation energies for defect movement during coincidence boundary migration in nickel oxide using computer simulation techniques

Two possible atomistic mechanisms of grain boundary migration in nickel oxide are examined for two coincidence boundaries using computer simulation techniques. In mechanism I, the boundary migrates by anion vacancy diffusion across it (calculated activation energy 0.64 eV in a (21̄1)/[011] boundary). In mechanism II, ions migrate across the boundary to add onto the opposite crystal lattice without the need for vacancies (activation energy 0.78 eV in a (12̄2)/[011] boundary and control by cation migration). The activation energy for an anion diffusion jump down a (21̄1)/[011] boundary is calculated as 1.57 eV. Anion vacancy supply down the boundary is therefore expected to be rate controlling for any migration mechanism requiring anion vacancies (i.e. mechanism I). There are few literature values for the grain growth activation energy in bulk NiO but values of ~0.9 eV are deduced from published data on grain sizes in NiO scales. 0.9 eV is low in comparison with literature values for a variety of ceramics. Comparison between 0.9 eV and the computer predicted activation energies for defect migration suggests that, unless the effective anion vacancy formation energy at a general grain boundary is considerably lower than expected, it is likely that anion vacancy formation is not required for boundary migration in NiO.     

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.     

Co/CeO2 for ethanol steam reforming： effect of ceria morphology

Nanorods (NR) and nanoparticles (NP) of ceria were prepared by hydrothermal synthesis method and used as catalyst support to load cobalt for steam reforming of ethanol (SRE). The catalysts were characterized by using temperature programmed reduction, X-ray diffraction, transmission electron microscopy and thermal analysis techniques. CeO₂ NP had relatively smaller particle size and larger surface area, and CeO₂ NR could form more oxygen vacancies. For SRE reaction, Co/CeO₂ NP was more active and exhibited a little better anti-sintering ability, while Co/CeO₂ NR showed obviously better anti-carbon deposition ability. The larger surface area and higher dispersion of cobalt oxide resulted in the higher activity for Co/CeO₂ NP catalyst. Meanwhile, the stronger interaction between cobalt species and ceria was attributed to the better anti-sintering ability for Co/CeO₂ NP. The improvement of the anti-carbon deposition for Co/CeO₂ NR was owing to the generation of oxygen vacancies from the ceria nanorods.     

A simulation of the NiO/Ag interface with point defects

The NiO/Ag interface has been modelled using established simulation techniques, which have been modified to include the image interactions between the oxide ions and the induced charge in the metal. The energies of point defects near the interface were calculated and it was found that the surface rumpling was such that defects with a negative net charge were favoured. This will result in a space charge layer with excess cation vacancies which will cancel the interfacial potential. A low energy interface was modelled in which the cation sub-lattice of the second oxide plane was saturated with vacancies and Ni³⁺ ions. Such a structure may be responsible for the observed excess of oxygen near the NiO/Ni interface, and also for the low wetting angles of metals on NiO, compared with MgO.     

Preparation and characterization of Ce1-x NixO2 as oxygen carrier for selective oxidation methane to syngas in absence of gaseous oxygen

A citric acid complex method was employed to prepare Ce/Ni mixed oxides with various Ce/Ni ratios useful for selective oxidation methane to syngas in the absence of gaseous oxygen, and the catalytic activity measurement was investigated in a fixed bed reactor at 800 °C. The prepared oxygen carriers were characterized by various characterization techniques such as TG-DSC, XRD and TPR. The results of TG-DSC indicated that the Ce_1-xNi_xO₂ precursor generated a stable phase after the heat-treatment at temperatures above 800 °C. The XRD characterization suggested that some Ce-Ni solid solution was formed when Ni²⁺ ions was incorporated into the lattice of CeO₂, and it led to the generation of O-vacancy which could improve the oxygen mobility in the lattice of oxygen carriers. It was found that Ce_0.8Ni_0.2O₂ gave the highest activity in the selective oxidation methane to syngas reaction, and the average methane conversion, CO and H₂ selectivity reached to 82.31%, 82.41% and 87.64%, respectively. The reason could be not only attributed to the fitting amount of NiO dispersed on the CeO₂ surface and bulk but also to actual lattice oxygen amount increased in oxygen carrier.     

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.     

Thermodynamics of Oxygen Solution in Fe–Ni Melts Containing Boron

Fe–Ni alloys are widely used in engineering today. They are sometimes alloyed with boron. Oxygen is a harmful impurity in Fe–Ni alloys. It may be present in dissolved form or as nonmetallic inclusions. The presence of oxygen in Fe–Ni alloys impairs their performance. Research on the thermodynamics of oxygen solutions in Fe–Ni melts containing boron is of considerable interest in order to improve alloy production. The present work offers a thermodynamic analysis of solutions of oxygen in Fe–Ni melts containing boron. The equilibrium constant of the reaction between boron and oxygen dissolved in the melt in such systems is determined. The activity coefficients at infinite dilution and the interaction parameters in melts of different composition are also calculated. When boron reacts with oxygen in Fe–Ni melts, the oxide phase contains not only B₂O₃ but also FeO and NiO. The mole fractions of B₂O₃, FeO, and NiO in the oxide phase are calculated for different boron concentrations in Fe–Ni melts at 1873 K. For iron melts with low boron content, the mole fraction of boron oxide is ~0.1. With increase in the nickel and boron content in the melts, the boron-oxide content in the oxide phase increases. Its mole fraction is close to one for pure nickel. The solubility of oxygen in Fe–Ni melts is calculated as a function of the nickel and boron content. The deoxidizing ability of the boron improve significantly with increase in nickel content in the melt. The curves of oxygen solubility in Fe?Ni melts containing boron pass through a minimum, which is shifted to higher boron content with increase in nickel content in the melt. The boron content at the minima on the curves of oxygen solubility are determined, as well as the corresponding minimum oxygen concentrations.     

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.     

Fabrication of NiO Buffer Layer for YBCO Coated Conductors by Combining Sputtering and SOE Method

In research of YBCO coated conductors, the development of a oxide template for epitaxial growth of YBCO is very important. Matsumoto et al have demonstrated the potential of the surface oxidation epitaxial (SOE) route for formation a cube textured NiO layer on nickel tapes. The epitaxial NiO functions as a buffer layer of chemical reaction between YBCO and nickel, and as a template for the epitaxial growth of YBCO. However, the surface quality of NiO is difficult to control and defects such as crack, spall and deep grooves exist in SOE NiO layer. A new approach combining sputtering and SOE method to obtain crack-free and cube textured NiO layer were reported. Ni tapes prepared by the combination of rolling and recrystallization were used for this work. A coating of Ni was first deposited on the tapes via magnetron sputtering. Then on the coating tapes, continuous and textured NiO layer were achieved by SOE technology.     

Stable NiO–CeO2 nanoparticles with improved carbon resistance for methane dry reforming

High surface area mixed oxide 8.7% NiO-CeO₂ nanoparticles (122 m²/g; 6–7 nm) were prepared using a reversed microemulsion method, and were tested for dry methane reforming (DRM). The catalytic activity of these nanoparticles remains stable under the severe conditions of DRM (700 °C), and they show better carbon resistance than conventional NiO-CeO₂ catalysts prepared without control of the size. The activity and selectivity of nanoparticles and reference catalyst are similar, but nanoparticles reduce the accumulation of carbon by 63% during the DRM tests, which is a key feature for this reaction. XPS and H₂-TPR suggest that the improved carbon resistance of the nanoparticles is due to the better interaction and cooperation between NiO and CeO₂ mixed phases. In nanoparticles, the participation of cerium cations in the redox processes taking place during DRM stabilizes cationic species of nickel. On the contrary, the catalyst prepared without control of the size suffers segregation of Ni during DRM reaction, and segregated Ni explains the higher catalytic formation of carbon.     

1723K下熔渣中Ni~(2+)和Fe~(2+)离子共存时的电化学行为

利用MgO部分稳定的ZrO_2固体电解质管集成构建以Pt,O_2(空气)|ZrO_2作为参比电极的新型可控氧流电解池,采用循环伏安CV、方波伏安SWV、恒电位电解PE等方法,并结合热力学计算与显微观察、能谱分析,研究1 723K高温下SiO_2-CaO-MgO-Al_2O_3熔渣中共存的Ni~(2+)、Fe~(2+) 离子在Ir电极上的电化学行为。结果表明:熔渣系中FeO与NiO之间存在较弱的相互作用,但镍离子以Ni~(2+)存在,铁离子基本以Fe~(2+) 存在。进行方波伏安分析时,Ni~(2+)、Fe~(2+) 离子的还原峰电流对频率呈现不同的规律。Ni~(2+)在Ir电极上的电化学还原是扩散控制的一步两电子转移反应过程;Fe~(2+) 到Fe的电化学还原也是一步两电子转移反应过程,但Fe~(2+) 的还原明显受到Ni~(2+)还原的影响。基于循环伏安法,计算得到NiO、FeO的质量分数分别为3%、5%的熔渣中Ni~(2+)离子在1 723K下的扩散系数为(9.2±0.2)×10-6cm2/s。     

Effect of La_2O_3on Methanation of CO and CO_2over Ni-Mo/γ-Al_2O_3Catalyst

In the early 1980s, it was reported thatrare earth oxide can improve the properties ofnickel catalysts['J. In this paper, the effect ofLaZO3 on activity of methanation of CO andCOb over Ni-Mo/Y-A12O3 was studied. The relationship between catalytic activity, surfacebehaviour and the role of LaZO3 in Mi-Mo-La/Y-Allot catalyst were investigated by means oftransmission electron microscope (TEM ), Xray photoelectron spectroscopy (XPS ), andchemisorption of CO.1 Experimental1. I Prepara…     

NiO-La2O3/γ-Al2O3催化剂中各组分间的相互作用

本文采用差热分析、X射线衍射、透射电镜和选区电子衍射对催化剂的物种情况及形貌加以研究 ,结合催化剂焙烧过程的相变情况 ,从而获得催化剂焙烧过程的化学反应情况。发现稀土助剂的加入使载体的晶体结构发生变化 ,从而使载体表面改性 ,抑制了 Ni Al2 O4的生成 ,提高了 Ni O的分散度。而且发现有 L a2 O2 CO3晶体存在于载体表面 ,L a2 O3以高度分散的状态存在     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.