Two Ce(SO4)2·4H2O polymorphs: Crystal structure and thermal behavior

Syntheses, crystal structures and thermal behavior of two polymorphic forms of Ce(SO₄)₂·4H₂O are reported. The first modification, α-Ce(SO₄)₂·4H₂O (I), crystallizes in the orthorhombic space group Fddd, with a=5.6587(1), b=12.0469(2), c=26.7201(3) Å and Z=8. The second modification, β-Ce(SO₄)₂·4H₂O (II), crystallizes in the orthorhombic space group Pnma, with a=14.6019(2), b=11.0546(2), c=5.6340(1) Å and Z=4. In both structures, the cerium atoms have eight ligands: four water molecules and four sulfate groups. The mutual position of the ligands differs in (I) and (II), resulting in geometrical isomerism. Both these structures are built up by layers of Ce(H₂O)₄(SO₄)₂ held together by a hydrogen bonding network. The dehydration of Ce(SO₄)₂·4H₂O is a two step (I) and one step (II) process, respectively, forming Ce(SO₄)₂ in both cases. During the decomposition of the anhydrous form, Ce(SO₄)₂, into the final product CeO₂, intermediate xCeO₂·yCe(SO₄)₂ species are formed.     

层状晶体β-MNCl(M=Zr,Hf)的电子掺杂新方法及其性质研究

通过控制叠氮化物RN_3(R=Li, Na, K, Rb)与层状晶体β-MNCl (M = Zr, Hf) 反应的摩尔比，成功地对层状晶体β-MNCl(M=Zr, Hf)进行了电子掺杂，得到了转 变温度分别是13.5K和23.5K的超导体。实验结果还进一步表明，当摩尔比x=n (NaN_3)/n(β-ZrNCl)=0.3时，反应所得反插层化合物ZrNCl_(1-x)经450 ℃退火处 理后，其超导性质最好。作者同时利用XRD，TEM和SQUID测试结果，分析了化学反 应机理和电子掺杂原理，并研究了所得超导体在空气中的稳定性。     

Doping Effect on the Grain Growth of Spinel LiMn2O4 Prepared by Sol-Gel Methods

The cathode-active materials, Li1+yMxMn2-xO4 (M = Al, Co, Ni, Zn, y = 0.02, x = 0.02) powder, were synthesized by sol-gel method using LiOH, Mn(NO3)2 as the starting materials, citric acid as a carrier and Al(NO3)3·9H2O or Co(NO3)2·6H2O or Ni(NO3)2·6H2O or Zn(NO3)2·6H2O as dopants. The influence of different doping elements on the structural properties of the as-prepared samples was investigated by X-ray diffraction (XRD), infrared (IR) spectroscopy and scanning electron microscopy (SEM). X-ray diffraction patterns of the prepared samples were identified as the spinel structure with space group Fd3m. The grain size increases gradually as the sintering temperature rises and corresponding activation energies for the grain growth have been estimated using Arrhenius’ empirical relation.     

Synthesis and electrochemical properties of LiNi0.9-xCo0.1SnxO2 as cathode materials for lithium secondary batteries

LiNi_0.9-x Co_0.1Sn _x O₂ (x = 0.00, 0.02, and 0.03) were synthesized via the rheological phase reaction method and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The sample of LiNi_0.9-x Co_0.1Sn _x O₂ (x = 0.02) not only shows good cycle performance but also exhibits an excellent discharge capacity of 188 mAh/g in the first cycle at a current density of 100 mA/g in the voltage range of 3.0–4.3 V. The tin doping results in reducing the resistance and increasing conductivity of LiNi_0.9-x Co_0.1Sn _x O₂. This composite oxide is promising as cathode material for lithium-ion battery.     

掺杂Ce的TiO_2纳米粒子的光致光及其光催化活性

采用sol-gel法制备了纯的和掺杂不同量Ce的TiO_2纳米粒子，并利用XRD， TEM，BET，XPS和PL光谱对样品进行表征，主要考察焙烧温度和含量对掺杂Ce的 TiO_2纳米粒子性质以及光催化降解苯酚活性的影响，并探讨了Ce的掺杂对TiO_2相 变的作用机制以及PL光谱与光催化活性的关系，结果表明，掺杂的Ce~(4+)没有进 入到TiO_2晶格中，而是以小团簇的CeO_2化学态均匀地弥散在TiO_2纳米粒子中， 这可能导致了Ce的掺杂对TiO_2的相变有很大的抑制作用；Ce的掺杂没有引起新的 光致发光现象，而适量Ce的掺杂能够降低TiO_2纳米粒子PL光谱的强度，这是因为 掺杂的Ce~(4+)易于捕获光生电子而生成Ce~(3+);600℃处理的掺杂Ce的TiO_2纳米 粒子表现出较高的光催化活性，这说明600℃是比较合适的焙烧温度，而掺杂不同 量的Ce的TiO_2样品的光催化活性顺序是：3 mol%＞4 mol%＞2 mol%＞5 mol%＞1 mol%＞0 mol%，这与它们的PL光谱强度的顺序是相反的，即PL光谱强度越低，其 光催化活性越高，这说明PL光谱与其光催化活性间有着必然的联系，这是因为掺杂 剂Ce~(4+)能够捕获光生电子，在光致发光过程中使PL光谱强度下降，而在光催化 反应过程中使有机污染物加快氧化。     

Property control of new forms of carbon materials by fluorination

Multiwall carbon nanotubes (MWNTs) based on the template carbonization technique were fluorinated in a temperature range 323-473 K by elemental fluorine. The fluorination of the carbon nanotubes results in functionalization and modification of pristine nanotubes with respect to adsorption and electrochemical properties. Selective fluorination of the inner surface of the carbon nanotubes, brings about a decrease in the surface free energy of the inner surface of the tubes and an increase in colombic efficiency of Li/nanotubes rechargeable cells in an aprotic medium. Electrochemical fluoride-ion doping of fullerene C₆₀ thin films (250-450 nm) was carried out in a fluoride-ion conductive solution, MeCN solution of 1 M Et₄NF·4HF. Galvanostatic oxidation yielded C₆₀F_ca.1-3 where fluorine exists as a semi-ionic species in the cavity surrounded by C₆₀ molecules without forming covalent CF bonds     

Surface characterization and thermodynamics of adsorption of Sr2+, Ce3+, Sm3+, Gd3+, Th4+, UO 2 2+ on activated charcoal from aqueous solution

Surface parameters of the activated charcoal were measured using precise instrumental techniques for dehydration, carbon content, trace metals impurities, anions, bulk, tap and true densities, surface area, pore volume, porosity and average particle diameter. The adsorption of Sr²⁺, Ce³⁺, Sm³⁺, Gd³⁺, Th⁴⁺ and UO ₂ ²⁺ ions on activated charcoal from aqueous solution was studied as a function of temperature. Thermodynamic parameters such as HH ⁰ and S ⁰ were calculated from the slopes and intercepts of the linear variation of lnK ₁ vs. 1/T, whereK ₃ is obtained from Langmuir equation. The results show endothermic heats of adsorption, but negative free energy values indicate that the adsorption process of metal ions on activated charcoal is favored at high temperature. The value of isosteric heat of adsorption, calculated from the Clausius-Clapeyron equation, shows that the surface of the activated charcoal is heterogeneous with respect to activity. A wavelength dispersive x-ray fluorescence spectrometer was used for measuring the concentration of metal ions.     

High-pressure synthesis, crystal structure and magnetic properties of a new cuprate (Nd,Ce)2+xCaCu2O6+y

New phase (Nd,Ce)_2+xCaCu₂O_6+y was prepared at a high-pressure/high-temperature condition of 6 GPa and 1300°C. It had a nonstoichiometric composition close to Nd_2.16Ce_0.225CaCu₂O_6+y. According to X-ray diffraction pattern, the Nd_2.16Ce_0.225CaCu₂O_6+y phase has a tetragonal lattice with a = 3.845(1) Å, c = 19.349(5) Å. However, electron microscopic observations revealed a complicated shear structure for this phase. Magnetic susceptibility and magnetic hysteresis measurements were performed for the Nd_2.16Ce_0.225CaCu₂O_6+y sample and it was found that the phase undergoes a weak ferromagnetic transition at 150 K. Below ≈40 K, complicated magnetic behavior was observed suggesting the presence of second weak ferromagnetic transition near 40 K.     

尖晶石LiMn2O4的改性研究

由于资源丰富、价格便宜、易制备、对环境无污染、可回收利用等优点,尖晶石型LiMn2O4成为锂离子二次电池中最有希望的正极材料[1~3]。然而,在高电压充、放电条件下,由于电极中锰的溶解和Jahn鄄Teller效应的发生,会造成LiMn2O4容量迅速衰减[4~6]。为了改善LiMn2O4的电化学性能,研究者主要通过优化合成条件及合成方法来控制产品的粒径分布与形貌,以利于锂离子的脱、嵌[7,8];用掺杂的方法以稳定其结构,抑制Jahn鄄Teller效应的发生[9,10];用表面修饰的方式来减少活性物质与电解液的直接接触从而降低Mn的溶解[11,12]。掺杂方面,Co3 不仅有…     

Vapor phase reduction of cyclohexanone to cyclohexanol on CexZr1-xO2 solid solutions

Reduction of cyclohexanone to cyclohexanol using propane-2-ol as hydrogen donor has been carried out in vapor phase on Ce_xZr_1-xO₂ solid solutions synthesized by ombustion synthesized at 302°C. The solid solutions around 0.4 mol% cerium content show better catalytic activity compared to pure ZrO₂ and the selectivity to cyclohexanol is 98%. A moderate acid-base and good redox properties of Ce_xZr_1-xO₂ solid solutions are seen to be responsible for the catalytic activity. A possible mechanism of hydride transfer has been proposed with cerium ions as promoters. This revised version was published online in June 2006 with corrections to the Cover Date.