Phase-change optical recording: Past, present, future

We discuss specific features of Te-based compounds that made them the best materials for the phase-change data storage. It is demonstrated that the phase-change recording is due to a switch of Ge atoms between octahedral and tetrahedral symmetry positions within the Te face-centered cubic lattice. It is this nature of the transition that makes the Te-based media fast and stable. The driving force for this transition is also discussed. The chapter is concluded by introduction of a concept of the super-resolution near-field structure (super-RENS) disc that allows to reduce a bit size well below the diffraction limit and makes 100 GB/disc storage a reality.     

Synthesis of LiFePO4 with fine particle by co-precipitation method

LiFePO₄ is a potential candidate for the cathode material of the lithium secondary batteries. A co-precipitation method was adopted to prepare LiFePO₄ because it is simple and cheap. Nitrogen gas was needed to prevent oxidation of Fe²⁺ in the aqueous solution. The co-precipitated precursor shows the high reactivity with the reductive gas, and the single phase of LiFePO₄ is successfully synthesized with the aid of carbon under less reductive conditions. LiFePO₄ fine powder prepared by co-precipitation method shows high rate capability, impressive specific capacity and cycle property.     

Synthesis and structural characterization of new defect pyrochlore type AxLnySb2O6+z antimoniates (0<x, y, z<1; A = Rb, Cs, Tl; Ln = Eu, Gd, and Y) prepared by coprecipitation

New cubic defect pyrochlore type A_xLn_ySb₂O_6+z antimoniates (0<x,y,z<1; A=Rb, Cs, Tl; Ln=Eu, Gd, and Y) (space group Fd3m) were prepared by calcination in air at 650 °C of compositions obtained by a coprecipitation method. Their crystal structures were refined by the Rietveld procedure and further confirmed by X-ray absorption spectroscopy (EXAFS) experiments. Refinements of the X-ray powder diffraction data show a partial and statistical occupation of the 8b site by alkaline or thallous ions and oxygen and lead to values close to 0.33 for the only refinable positional x parameter of the 48f oxygenated site.     

Preparation of nickel-tungstate catalysts by a novel impregnation method

Nickel-tungstate/γ-alumina (NiW) catalysts were prepared by an incipient wetness impregnation method using citric acid as a complexing agent. Citric acid has been used by our research group in preparing cobalt-molybdate and nickel -molybdate catalysts. The extended X-ray absorption fine structure (EXAFS) data of the impregnating solutions indicated that citric acid contributes to the formation of polytungstate anions that are smaller than the dodecatungstate ions formed when conventional ammoniacal solutions are used. Sulfided NiW catalysts prepared by using citric acid showed higher hydrogenation activity and hydrogenation selectivity than NiW catalysts prepared using the conventional ammoniacal solutions.     

A new synthesis procedure for titanium-containing zeolites under strong alkaline conditions and the catalytic activity for partial oxidation and photocatalytic decomposition

A new synthesis procedure for titanium-containing aluminosilicate zeolites has been obtained using a clear colloidal dispersion (sol) which was prepared with titanium isopropoxide, water, hydrochloric acid and colloidal silica, Ludox. When NaY, KL, offretite, mordenite and ZSM-5 zeolites were crystallized from the sol following conventional hydrothermal crystallization procedures, all the aluminosilicate zeolites showed the same X-ray absorption fine structure at the Ti K edge indicating framework Ti. The zeolites showed remarkable catalytic activity for the partial oxidation of cyclohexene using H₂O₂ as an oxidant and the photocatalytic decomposition of trichloroethene using water.     

AKIMA方法在EXAFS谱解析中的应用

解析扩展Ｘ射线吸收精细结构谱（ＴｈｅＥｘｔｅｎｄｅｄＸ－ｒａｙＡｂｓｏｒｐｔｉｏｎＦｉｎｅＳｔｒｕｃｔｕｒｅＥＸＡＦＳ）的一种方法是曲线拟合，在曲线拟合中，能量阈值Ｅ０的确定有着很重要的意义，同时也有相当的难度，本文应用ＡＫＩＭＡ平滑数据点方法达到了对Ｅ０在数学意义上的精确求解，数据分析结果表明，这种方处理结果是令人满意的。     

尖晶石纳米催化剂应用于烯丙醇多相氧化制烯丙醛或烯丙酮

使用共沉淀法通过Ru对MeFe2O4的同晶取供制备了纳米级MnFe1.95Ru0.05O4催化剂。在通过过渡金属进一步改性该催化剂的过程中，发现MnFe1.95Ru0.05O4的催化剂性能优异于文献报道的其他多相醇氧化催化剂，XRD测试表明该催化剂仍保持尖晶石结构。该纳米催化剂能有效地将不同烯丙醇类氧化成烯丙醛类或烯丙酮类，与文献报道的其他多相氧化催化体系相比，该催化剂具有更高的活性转换数。借助于EXAFS等表征结果和1－辛醇与4－辛醇的竞争反应，判断出单核的Ru类反应的活性中心，EXAFS的表征同时表明由于Cu的添加而产生的Ru=0能加快反应速率。作者在此基础上提出反应机理，认为Ru在反应过程中形成醇化物，再经过β消除反应生成相应的醛或酮。     

Sintering of Pt/Al2O3 reforming catalysts: EXAFS study of the behavior of metal particles under oxidizing atmosphere

The effect of an oxidative atmosphere (300 °C) is studied on fresh and sintered unchlorinated naphtha reforming catalysts containing 0.6–1% Pt. The TPR profiles show that only one species is formed using our experimental conditions, regardless of the mean crystallite size of the metal particles. The structural information supplied by EXAFS compared with cuboctahedral particle modeling, implies that such species is a surface platinum oxide, the structure of which is close to that of PtO₂, but largely distorted. This is true whether the catalyst is sintered or not.     

EXAFS and XPS Investigations of Cu/ZnO Catalysts and Their Interaction with CO and Methanol

Several investigations have been carried out on Cu/ZnO catalysts by employing extended Xray absorption fine structure (EXAFS) and Xray photoelectron spectroscopy (XPS). EXAFS investigations of Cu/ZnO catalysts subjected to hydrogen reduction show the presence of Cu¹⁺ species and Cu microclusters. The proportion of Cu¹⁺ depends on the rate of increase of the reduction temperature and on the amount of alumina added. An XPS study of the interaction of CO with model Cu/ZnO catalysts prepared in situ in the electron spectrometer shows the formation of CO₂ ^-, CO₃ ^2- and C₂O₄ ^2- species, their proportion relative to CO increasing with the Cu¹⁺/Cu⁰ ratio. A study of the interaction of CH₃OH with Cu clusters deposited on ZnO films reveals reversible molecular adsorption and the formation of CH₃O on clean Cu clusters. If the Cu clusters are pretreated with oxygen, however, both CH₃O and HCOO^- species are produced. Model Cu/ZnO catalyst surfaces containing both Cu¹⁺ and Cu⁰ species show interesting oxidation properties. On a Cu⁰-rich catalyst surface, only the CH₃O species is formed on interaction with CH₃OH. On a Cu¹⁺rich surface, the HCOO^- ion is the predominant species.     

An EXAFS study on oxidic and sulfided K-MoO3/γ-Al2O3 catalysts

By analyzing the extended X-ray absorption fine structure (EXAFS) of the Mo K-absorption edge, structural information for both oxidic and sulfided K-MoO₃/-Al₂O₃ catalysts with different potassium content was obtained. The oxidic samples show two backscatterer peaks in the radial distribution function (RDF), which correspond to the Mo-O coordinations in the nearest Mo-O shell. The nearest oxygen atoms are present with large configurational disorder. The RDF for the K/Mo = 0 sample is significantly different from that for crystalline MoO₃ and ammonium heptamolybdate. The RDFs for potassium promoted samples are, in some extent, similar to that for ammonium heptamolybdate. The sample with K/Mo = 0.8 and that with K/Mo=1.5 do not show obvious difference in their local Mo-O structures. The EXAFS results support the earlier conclusions from Raman spectroscopy studies on identical samples [7]. When the samples are sulfided, a rearrangement of the local neighbors around Mo atoms takes place, to form small MoS₂-like crystallites. The Mo-S and Mo-Mo coordination distances on these catalysts are the same as those in crystalline MoS₂, but the coordination numbers are significantly lower than in MoS₂. The EXAFS results indicate that Mo species on the K/Mo=0 catalyst mainly consist of Mo-S-Mo units (the basic building units of MoS₂), which are highly dispersed and show a higher level of disorder than in MoS₂. With the modification by the potassium promoter, Mo species are significantly aggregated and their local neighbors are more similar to those in MoS₂, but the Mo species still exist in a state of high dispersion.