反应扩散法制备的PbMo6S8超导带的超导特性

本文报道反应扩散法制备Chevrel相PbMo₆S₈超导带材的过程以及带材的超导特性。Mo带与H₂S气体反应生成单相的Mo-S化合物(MoS₂或Mo₂S₃,根据反应温度而定),再与Pb的蒸汽反应生成单相的PbMo₆S₈薄层。PbMo₆S₈超导层的临界温度T_c=13.0 关键词：     

Chevrel相M_xMo_6S_8化合物电荷转移和Mo原子上4d轨道能级的分裂

本文用配位场方法导出了Chevrel相M_xMo_6S_8化合物中M和Mo_6S_8原子簇间电荷转移和Mo原子上4d轨道能级分裂的解析关系。结合PbMo_6S_8的反射光谱,求得Mo_6S_8原子簇至Pb的电子转移数为1.18,和以前一般文献上认为的两个电子从Pb转移至Mo_6S_8不同。Mo_6上的4d电子数为18.8。     

水热法制备Mo1-XWXS2合金材料及晶体结构的研究

采用水热合成法制备合金半导体材料Mo_1-XW_XS₂（X为浓度）,并应用扫描式电子显微镜（SEM）、X射线衍射（XRD）和拉曼光谱仪（Raman）对其形貌和晶体结构进行表征。实验结果表明,由SEM形貌测试发现,随着掺杂浓度的增加,Mo_1-XW_XS₂片状合金材料表面逐渐粗糙;由XRD晶体结构表征发现,随着掺杂浓度的增加,Mo_1-X W_XS₂的晶格常数逐渐增大;在合金材料的拉曼频移中,随着掺杂浓度的增加,Mo_1-XW_XS₂中A_1g振动模发生蓝移,而E¹_2g振动模发生红移。通过晶格结构和拉曼频移的检测和分析,证实水热合成法可制备不同浓度的Mo_1-XW_XS₂合金半导体材料。本方法可进一步拓展为二硫族化物合金...     

Bi2S3/BiOCl复合光催化剂的水热合成及其高活性

采用一种简便的水热法在433 K的温度下成功合成了具有不同Bi₂S₃质量分数的Bi₂S₃/BiOCl复合光催化剂,利用各种技术对其进行了表征.在紫外光照射下,以甲基橙水溶液的光催化降解为模型反应,评价了Bi₂S₃/BiOCl复合光催化剂的活性.研究结果表明:与纯Bi₂S₃和纯BiOCl相比,Bi₂S₃/BiOCl样品明显具有更高的光催化性能,尤其当Bi₂S₃在Bi₂S₃/BiOCl中的质量分数为26.5%时,Bi₂S₃/BiOCl复合催化剂的光催化活性与商业P25(TiO₂)的活性非常接近,而这种商业P25在紫外光照射下是公认的高效光催化剂.这种明显提高的光催化活性主要归功于光生电子和空穴在Bi₂S₃和BiOCl形成异质结界面上的有效转移,降低了电子-空穴对的复合.     

原子簇La8-xBaxCuO6的原子磁矩和自旋极化的电子结构研究

利用MS-Xα方法研究了化合物La_2-yBa_yCuO₄的原子磁矩和自旋极化的电子结构.理论计算得到母相氧化物La₂CuO₄的Cu原子磁矩为0.37μ_B，与实验值0.48±0.15μ_B基本一致. 研究结果显示, 由于Ba原子对部分La的替代，使构成化合物的基本原子簇La_8-xBa_xCuO₆的 关键词： 电子结构 自旋极化 磁矩 态密度 超导电性     

含有不同硫族元素原子比例的单层MoSSe电化学Pourbaix相图

MoSSe材料是一种非常有前途的光电材料,它的应用环境会接触到水溶液,但目前尚未有关MoSSe材料在水溶液中电化学稳定性的研究.本文基于密度泛函理论构建不同钼、硫和硒元素原子比例的单层MoSSe的Pourbaix图,研究在不同pH和电极电位条件下的热力学稳定性和电化学腐蚀行为.对MoSSe的Pourbaix图研究表明,一部分MoSSe的免蚀区域存在于Pourbaix图中水的稳定区域内,说明MoSSe在水环境中可以稳定存在;相比较碱性溶液来说,MoSSe在酸性和中性溶液中的耐腐蚀性更好.对Mo₄S₂Se₆,Mo₄S₆Se₂,Mo₄S₇Se和Mo₄SSe₇的Pourbaix图研究表明,在不同钼、硫和硒元素原子比例的单层MoSSe中硫的物质的量浓度较高的情况下,材料在水溶液中可以稳定存在的条件范围变大,耐腐蚀性变好;在不同钼、硫和硒元素原子比例的单层MoSSe中硒的物质的量浓...     

P2S5/NH4OH处理GaAs(100)表面的电子能谱研究

采用俄歇电子能谱(AES)和X射线光电子能谱(XPS)研究了P₂S₅/NH₄OH钝化液处理的GaAs(100)表面的微观特性。AES测量表明,在钝化膜和GaAs衬底之间的界面处无O组分,只有P和S组分。XPS测量分析指出,经过P₂S₅/NH₄OH溶液处理后,GaAs表面处Ga₂O₃和As₂O_{3关键词：}     

光折变法制备的As2S8条形波导的光阻断效应

实验研究了As₂S₈薄膜光折变现象.提出并采用紫外光激励的方法试制了As₂S₈条形波导，导模激励显示该波导具有良好的导波特性.在此基础上，考察了As₂S₈条波导的光阻断效应，实现了光-光效应的开关功能. 关键词： 光波导技术 2S₈条形波导')" href="#">As₂S₈条形波导 光阻断效应 光激励法     

NaCu5S3复合NixFe-LDH的结构对水解氧析出性能的影响

析氧反应(OER)在锌空气电池、燃料电池和电解水等能源储存和转换设备中都有至关重要的作用.然而OER过程涉及四电子转移,导致反应动力学缓慢.尽管贵金属氧化物被认为是最先进的OER电催化剂,但昂贵的价格以及稀缺性限制了其商业应用.因此,本工作结合水热和水浴法制备了NaCu₅S₃@Ni_xFe-LDH(x=1,2,3,4)纳米片阵列复合电催化剂.对样品的结构进行了表征,结果显示NaCu₅S₃和Ni₂Fe-LDH充分混合,形成紧密结合的界面,有利于电荷的快速转移,这将增强两相界面处的电子调控作用,改变其局域结构特性,促进OER电催化性能.电化学测试结果显示,当电流密度为20 mA·cm^-2时,NaCu₅S₃@Ni₂Fe-LDH在1.0 M KOH电解液中的氧析出过电位仅为227 mV,电催化性能优于原始的NaCu₅S₃(271 mV)...     

Ru13原子簇基态的磁性

采用离散变分局域自旋密度泛函方法，研究了三种可能的高对称几何构型的由１３个钌原子组成的Ru₁₃原子簇的电子结构．结果表明，所有具有不同对称性的Ru₁₃原子簇在它们各自的平衡位置处都有两重磁性解，从能量上看，每一种构型的低自旋解都比高自旋解更为稳定．基态原子簇为Ｉ_hRu₁₃原子簇，具有４μ_B的磁矩，或每个原子具有０.３１μ_B的磁矩．这与实验测得的Ru₁₃原 关键词：     

Superconducting thin films of MxMo6S8 type

Thin films of M_xMo₆S₈, where M=Pb, Sn, Sn-Al and Cu, known as the Chevrel phases have been prepared by d.c. getter sputtering method and the optimal conditions of their preparation have been determined. The transition temperatures reached: 10.16, 13.66, 11.74 and 12.86 K for thin films with M=Cu, Sn, Sn-Al and Pb respectively. The highest critical fields H_c²(0) of 428 kG were obtained for Pb compounds.     

Electronic properties of Bi2O3 and MoO3 and relationships to oxidation catalysis

A semiempirical atom superposition and electron delocalization molecular orbital analysis of the bonding and electronic structure of MoO₃, oxygen deficient MoO₃, and the α, β, and δ phases of Bi₂O₃ has been made. It is found that both small — e.g. MoO₆ — and large — e.g. Mo₆O₂₄ — clusters are useful models for cation electronic structure within the theory used. From the calculations, an interpretation is given for all available optical and photoemission data for the oxides. The color, conductivity, and new photoemission peak of oxygen-deficient MoO₃ conducting bronzes are found to be due to the addition of electrons to the lowest of three Mo 5d bands which are empty in MoO₃. Weakly allowed d ← d transitions in the red are responsible for the color. Strongly allowed Mo 5d ← O 2p charge transfer excitations are responsible for the optical absorption above 3.2 eV. For the bismuth oxides, three occupied bands are found showing strong Bi 6s, 6p, 6d and O 2p hybridization. These bands have been seen experimentally. The highest band surprisingly has Bi 6p lone-pair character which is explained in terms of the relative Bi 6s and 6p and O 2p ionization potentials using perturbation theory. Rather similar electronic structures are found for the three phases despite their varying cation coordinations and structures. A charge transfer optical absorption edge at ～ 2.6 eV for the β form agrees well with observations reported in the literature, and similar edges should occur for the other phases. The cubic δ form has an unusual low-lying band suggesting absorption in the infrared. Our results provide insight into the surface properties of these oxides.     

Electronic properties of Chevrel phases by positron angular correlation

A comparative study of the Chevrel phases Mo₆S₈, Mo₆Se₈, PbMo₆S₈ and Cu_1.8Mo₆S₈ is made by the positron angular correlation technique at room temperature. Electronic properties like the number of conduction electrons per cluster, the density of states at the Fermi level, the electron effective masses and the Fermi velocities are obtained within the framework of the free electron model. The results are discussed in terms of available theoretical and other experimental data.     

Preparation and mass transport properties of Li2.3Mo6S7.7

Unsuccessful attempts were made to prepare Li_xMo₆S_7.7 by direct ionic exchange of Cu₂Mo₆S_7.7 using aqueous, acetontrille, and molten salt solvents. Li_2.3Mo₆S_7.7 was eventually prepared by lithiation of Mo₆S₈ using n-butyl lithium reagent. The mass transport properties of hot-pressed samples were measured using a four-point dc technique and the following values at 415°C for the lithium ionic conductivity, .4×10⁻⁴ (ohms cm⁻¹) and lithium chemical diffusion coefficient 3.5×10⁻⁷ cm²/s, were derived. A possible explanation for the relatively low lithium ion mobility in Li_2.3Mo₆S_7.7 is discussed.     

Magnetic ordering in the superconducting state of rare earth molybdenum sulphides, (RE)1.2Mo6S8 (RE = Tb, DyandEr)

The resistance and ac susceptibility measurements on Tb_1.2Mo₆S₈, Dy_1.2Mo₆S₈ and Er_1.2Mo₆S₈ revealed a magnetic ordering in their superconducting state at 0.9, 0.4 and 0.15 K, respectively. Some of the important features of the ordering in each compound are discussed with reference to their upper critical field curves.     

Salting-out in intercalation compounds: Removing copper from Cu3Mo6S8 by intercalating lithium

We study the removal of the copper in Cu₃Mo₆S₈ by the intercalation of lithium. For 0<×<1, Li_xCu₃Mo₆S₈ is a single phase compound. For x?1, the copper atoms are forced out of the Mo₆S₈ host. We present a lattice-gas model which shows how the intercalation of Li can force the Cu out of the host.     

Superconductivity in the RexMo6S8

The rare earth molybdenum sulfides RE_xMo₆S₈ (RE = rare earth) have been synthesized and are found to be superconducting with a few exceptions. This result, which is surprising in view of the high concentration of magnetic ions, is correlated with the particular structure of these compounds based on on units of Mo₆S₈.     

Charge transfer and valence electron concentration in Chevrel phases

Single crystal X-ray diffraction measurements on M_xMo₃S₄ compounds (M = Cu, Ag, Sn, In) yield evidence for the existence of a charge transfer from the interstitial element M to the Mo₆S₈ building blocks. The importance of this transfer was estimated from the contraction of the Mo₆ octahedron as a function of the valency and the concentration of the cations. It is suggested that this effect stabilises the structure and has a strong influence on the superconducting transition temperature. Bonding is discussed using a simple valence bond model which is based on the electron requirement of the Mo₆ octahedron to form 12 covalent bonds.     

Synthesis and physical properties of new superconducting Chevrel phases HgxMo6S8

New ternary molybdenum chalcogenides Hg_xMo₆S₈ (0 < x < 1) have been synthesized and investigated for their structural, magnetic, and superconducting behavior. These new phases prepared at low temperature by reaction of mercury with Mo₆S₈ (obtained from oxidation of Cu₂Mo₆S₈ by iodine) have been characterized by x-ray diffraction, static Faraday susceptibility, and superconducting transition temperature studies. HgMo₆S₈ crystallizes in the rhombohedral space group $\text{R}\text{3 (}\text{a}{}_{\mathrm{r}}\text{= 6.51}\text{A}\text{?}\text{, α}{}_{\mathrm{<mtext>r</mtext>}}\text{= 92.53°)}$, has a paramagnetic, temperature dependent susceptibility, and superconducts at 8.1K. As the mercury content decreases, a continuous decrease in T_c from 8.1K to 1.7K for x=0 (Mo₆S₈) is observed.