The role of CeO2-ZrO2 as support in the ZnO-ZnCr2O4 catalysts for autothermal reforming of methanol

Autothermal reforming of methanol for hydrogen production was investigated over ZnO-ZnCr2O4 supported on a series of metal oxides (Al2O3, CeO2, ZrO2 and CeO2-ZrO2)CeO2-ZrO2 mixed oxides with Ce /Zr molar ratio of 4/1 was found to be the optimal support which showed significant effect on the catalytic activity and selectivity. The ZnO-ZnCr2O4/CeO2-ZrO2 and ZnO-ZnCr2O4 catalysts were characterized by XRD, TEM, H-2-TPR and XPS. The results show that CeO2-ZrO2 mixed oxides have significant effect on the catalytic performance and the supported catalyst shows more uniform temperature distribution in the catalyst bed which was mainly due to its reasonable redox properties.

Catalytic steam reforming of ethanol to produce hydrogen and acetone

Steam reforming of ethanol over CuO/CeO2 was studied. Acetaldehyde and hydrogen were mainly produced at 260degreesC. At 380degreesC, acetone was the main product, and 2 mol of hydrogen was produced from 1 mol of ethanol. The formation of hydrogen accompanied by the production of acetone was considered to proceed through the following, consecutive reactions: dehydrogenation of ethanol to acetaldehyde. aldol condensation of the acetaldehyde, and the reaction of the aldol with the lattice oxygen [O(s)] on the catalyst to form a surface intermediate, followed by its dehydrogenation and decarboxylation. The overall reaction was expressed by2C(2)H(5)OH + H2O --> CH3COCH3 + CO2 + 4H(2). Ceria played an important role as an oxygen supplier. The addition of MgO to CuO/CeO2 resulted in the production of hydrogen at lower temperatures by accelerating aldol condensation. (C) 2004 Elsevier B.V. All rights reserved.

CuO,CuCl对P2O5-ZnO-Na2O玻璃性质的影响

包边技术是提高大尺寸激光玻璃饱和增益系数的关键。为获得优质包边玻璃,以CuO和CuCl分别作为Cu2+的引入物质,采用传统的玻璃熔制方法,研究了Cu2+掺杂量和不同引入物质对P2O5-ZnO-Na2O体系玻璃形成区、析晶稳定性、物化性能以及吸收系数的影响。研究结果表明,CuO和CuCl都能增大P2O5-ZnO-Na2O体系的玻璃形成区、提高玻璃样品的析晶稳定性。玻璃样品的吸收系数随Cu2+掺杂浓度的增加而明显增大,当Cu2+掺杂摩尔分数达到6%时,样品在1053 nm处的吸收系数为59.46 cm-1,基

Growth of CeO2 : Bi12SiO20 crystals in multi-position furnace(II) - Space growth experiment

Ce-doped Bi12SiO20 single crystal with size of phi10mm x 40mm was successfully grown in space on board of the spacecraft Shenzhou No.3. The surface morphology of space-grown crystal is different from that of ground-grown crystal The space- and ground-grown crystals were measured by X-ray rocking curves, absorption spectra and micro-Raman spectra. The results show that the quality of Ce-deped crystal grown in space is better than that of the ground-grown one. The effect of doping on optical properties of BSO grown in space is evident in comparison with the ground-grown crystal.

Violet/blue photoluminescence from CeO2 thin film

CeO2 thin film was fabricated by dual ion beam epitaxial technique. The violet/blue PL at room temperature and lower temperature was observed from the CeO2 thin film. After the analysis of crystal structure and valence in the compound was carried out by the XRD and XPS technique, it was inferred that the origin of CeO2 PL was due to the electrons transition from Ce4f band to O2p band and the defect level to O2p band. And these defects levels were located in the range of 1 eV around Ce4f band.

Growth and photoluminescence of epitaxial CeO2 film on Si (111) substrate

A CeO2 film with a thickness of about 80nm was deposited by a mass-analysed low-energy dual ion beam deposition technique on an Si(111) substrate. Reflection high-energy electron diffraction and x-ray diffraction measurements showed that the film is a single crystal. The tetravalent state of Ce in the film was confirmed by x-ray photoelectron spectroscopy measurements, indicating that stoichiometric CeO2 was formed. Violet/blue light emission (379.5 nm) was observed at room temperature, which may be tentatively explained by charge transitions from the 4f band to the valence band of CeO2.

A study of the interface of CeO2/Si heterostructure grown by ion beam deposition

Epitaxial cerium dioxide films on single-crystal silicon substrates (CeO2/Si) have been grown by a dual mass-analyzed low-energy ion beam deposition (IBD) system. By double-crystal X-ray diffraction (XRD), Full Width at Half Maximum (FWHM) are 23' and 33' in the rocking curves for (222) and (111) faces of the CeO2 film, respectively, and the lattice-mismatch Delta a/a with the substrate is about - 0.123%. The results show that the CeO2/Si grown by IBD is of high crystalline quality. In this work, the CeO2/Si heterostructure were investigated by X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) measurements. Especially, XPS and AES depth profiling was used to analyze the compositions and structures in the interface regions of the as-grown and post-annealed CeO2/Si. It was found that there was no silicon oxide in the interface region of the as-grown sample but silicon oxide in the post-annealed sample. The reason for obtaining such high quality heterostructure mainly depends on the absence of silicon oxide in the surface at the beginning of the deposition. (C) 1998 Elsevier Science Ltd. All rights reserved.

Identification of induced reaction during XPS depth profile measurements of CeO2/Si films grown by ion beam epitaxy

An anomalous behavior was observed in X-ray photoelectron Spectroscopy (XPS) depth profile measurements conducted on CeO2/Si epilayers grown by ion beam epitaxy (IBE): the signals of Ce3+ and Ce4+ co-exist, and the ratio between them increases during the etching time and then tends to maintain a constant level before increasing again. The results of X-ray Diffraction (XRD), Auger Electron Spectroscopy (AES), and Rutherford Back-Scattering (RES) measurements proved that the reduction chemical reaction of CeO2 is induced by ion-etching. (C) 1998 Elsevier Science Ltd. All rights reserved.

Mechanism of induced reaction during XPS depth profile measurements of CeO2/Si films grown by ion beam epitaxy

In a search for the mechanism of the induced reduction reaction that occurred in X-ray photoelectron Spectroscopy (XPS) depth profiles measured experimentally on CeO2/Si epilayers grown by ion beam epitaxy (IBE), several possibilities have been checked. The first possibility, that the X-ray induces the reaction, has been ruled out by experimentation. Other possible models for the incident-ion induced reaction, one based on short-range interaction (direct collision) and the other based on long-range potential accompanied with the incident-ions, have been tested by simulation on computer. The results proved that the main mechanism is the former, not the latter. (C) 1998 Elsevier Science Ltd. All rights reserved.

I：新型稀土永磁材料Nd-Fe-B氧化过程及抗氧化新体系研究II：CuO、Y_2Cu_2O_5、BaCuO_2和RBa_2Cu_3O_(7-δ)超导体磁化率及Cu价态研究

本论文由两大部分组成。第一部分是新型稀土永磁材料Nd-Fe-B氧化过程及抗氧化新体系的研究。Nd-Fe-B永磁体是1983年问世的新型稀土永磁材料。和原有的铁氧体及Sm-Co体系相比，具有磁能积高（50MGOe）。价廉源广，制备简单等三大优点；也有居里温度低（310℃），温度系数大（－0.126%/K），易氧化等三大缺点，我们对Nd-Fe-B合金的氧化过程进行研究，发现该材料热稳定性差，容易发生氧化反应，氧化使材料的结构受到破坏，并给材料的磁性造成不可恢复的损失，整个氧化过程是分阶段的。在室温和干燥的空气中材料基本是稳定的。150℃以下材料磁性受到破坏的主要原因是体系中Nd的氧化。230℃以上材料主体成分Fe也开始氧化，温度升高使反应进程大大加快。到800℃左右反应基本结束，最终产物主要为Fe_2O_3, Nd_2O_3·FeNdO_3和NdBO_3。增加体系中B的相对含量和添加某些新的元素均能提高材料的抗氧化能力，新研制的Nd-Fe-B-Si四元体系和原来的Nd-Fe-B体系相比具有下列显著优点：新体系的抗氧化能力大大提高，经过150℃的长期恒温试验，材料的结构，磁性均未受到破坏，某些体系甚至能在更高的温度下使用，另外，新体系的居里温度Tc也大为提高。比原有Nd-Fe-B磁体高40℃左右。因此该体系是一种大有发展前途的新材料。此外，我们用动态热重法研究了Nd-Fe-B合金的氧化动力学过程，但由于我们新合成的体系构相较为复杂，未能达到预期效果。第二部分是CuO，Y_2Cu_2O_5，BaCuO_2和RBa_2Cu_3O_(7-δ)超导体（R稀土元素）磁化率及铜价态研究，铜的氧化物具有复杂的化学计量关系和磁学性质。在对CuO的磁化率研究中，我们发现在低温区（77K－110K）和一定磁场下，CuO由顺磁突变为抗磁。这种转变与磁场强度有很大关系。这一结果与前人的工作有较大的出入。而与超导体的形为极为相似。所不同的是，转变温度与样品的重量也有关系。实验结果重复。由于铜氧性质在R-Ba-Cu-O超导体中起决定作用，因此有必要对CuO的低温磁性作进一步研究。此外，我们对文献尚未报道的Y_2Cu_2O_5的磁化率在77－300K温度区间进行了测量，发现它是顺磁性物质，室温有效磁矩μ_(eff) = 2.13μB。高于Cu~(2+)的理论有效磁矩（1.73μB）。经过碘量法价态分析，发现Y_2Cu_2O_5中有部分Cu~(3+)，这与磁化率的测定相符合。Tc在90K左右的Y-Ba-Cu-O体系是近期才发现的具有超高温超导材料。该体系有着独特的结构和性质。在对R-Ba-Cu-O及R-Ba-Cu-O-Ag超导体的研究中，我们发现此类超导体属II类超导体，在临界温附近该超导体由顺磁转变为抗磁，此种变化与磁场强度有很大关系，当场强大于一定值后，则观察不到这种转变。在对RBa_2Cu_3O_(7-δ) (R = Y, Sm, Eu, Gd, Dy, Ho, Er, Tm)超导体和具有相同配比但由于合成工艺条件不同而不超导的R'Ba_2Cu_3O_(7-δ) (R' = Y, Sm, Eu, Gd)非超导体的铜价态分析中，我们发现此两类化合物中均含有一定量的Cu~(3+)。且超导体中Cu~(3+)的含量高于非超导体中Cu~(3+)的含量（同样比例）。我们还发现Cu~(3+)对水极为敏感，将RBa_2Cu_3O_(7-δ) (除R = Gd, Dy, Er)超导体在未干燥容器中测出的Cu~(3+)量远远低于干燥容器中所测得的值。我们认为这可能是引起超导体不稳定的重要原因。由于尚缺乏用其它手段检测到超导体中Cu~(3+)存在的例证。故对此问题还有待于今后继续作进一步的研究。

High quality CeO2 film grown on Si(111) substrate by using low energy dual ion beam deposition technology

By using the mass-analyzed low energy dual ion beam deposition technique, a high quality epitaxial, insulating cerium dioxide thin film with a thickness of about 2000 Angstrom, has been grown on a silicon (111) substrate. The component species, cerium and oxygen, are homogeneous in depth, and have the correct stoichiometry for CeO2. X-ray double-crystal diffraction shows that the full width at half maximum of the (222) and (111) peaks of the film are less than 23 and 32 s, respectively, confirming that the film is a perfect single crystal. (C) 1995 American Institute of Physics.

CeO2/Si薄膜的紫／蓝光跃迁

利用双离子束外延技术制备了CeO2/Si薄膜，观察到了CeO2室温蓝光发光以及低温紫光致发光(PL)现象．利用XRD和XPS对薄膜结构及价态进行分析后表明，Ce02的发光机制是由于电子的Ce4f→O2p跃迁和缺陷能级→O2p能级跃迁共同作用的结果，并且这些缺陷能级位于Ce4f能级上下1eV的范围内．