SrIr9In18 – A Structurally Complex Intermetallic Compound with Sr@Ir4In12, Ir@In8 and Ir@In9 Building Units

Single crystals of SrIr₉In₁₈ were obtained by induction melting of the elements in a glassy carbon crucible followed by annealing at 1070 K. SrIr₉In₁₈ was structurally characterized by X-ray powder and single crystal diffraction: P4 m2, a = 811.21(5), c = 854.49(5) pm, wR₂ = 0.0511, 1223 F² values, and 46 variables. The structure is of a new type. The basic building units are Ir@In₈ (distorted square-prismatic, square anti-prismatic and bicapped trigonal prismatic coordination) and Ir@In₉ (distorted trigonal prismatic coordination) polyhedra, which condense to a three-dimensional network, which leaves large cavities for the strontium cations, which are coordinated to four iridium and twelve indium atoms. The [Ir₉In₁₈]^2– polyanionic network is stabilized through Ir–In (267–290 pm) and In–In (302–354 pm) bonding.     

具有优异甲醇耐受性的Rh掺杂PdCu有序金属间化合物纳米粒子增强氧还原电催化

Direct methanol fuel cells (DMFCs), as one of the important energy conversion devices, are of great interest in the fields of energy, catalysis and materials. However, the application of DMFCs is presently challenged because of the limited activity and durability of cathode catalysts as well as the poisoning issues caused by methanol permeation to the cathode during operation. Herein, we report a new class of Rh-doped PdCu nanoparticles (NPs) with ordered intermetallic structure for enhancing the activity and durability of the cathode for oxygen reduction reaction (ORR) and achieving superior methanol tolerance. The disordered Rh-doped PdCu NPs can be prepared via a simple wet-chemical method, followed by annealing to convert it to ordered phases. The results of transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), power X-ray diffraction (PXRD) analysis and high resolution TEM (HRTEM) successfully demonstrate the formation of near-spherical NPs with an average size of 6.5 ± 0.5 nm and the conversion of the phase structure. The complete phase transition temperatures of Rh-doped PdCu NPs and PdCu are 500 and 400 ℃, respectively. The molar ratio of Rh/Pd/Cu in the as-synthesized Rh-doped PdCu NPs is 5/48/47. Benefitting from Rh doping and the presence of the ordered intermetallic structure, the Rh-doped PdCu intermetallic electrocatalyst achieves the maximum ORR mass activity of 0.96 A·mg^-1 at 0.9 V versus reversible hydrogen electrode (RHE) under alkaline conditions—a 7.4-fold enhancement compared to the commercial Pt/C catalyst. For different electrocatalysts, the ORR activities follow the sequence, ordered Rh-doped PdCu intermetallics > ordered PdCu intermetallics > disordered Rh-doped PdCu NPs > disordered PdCu NPs > commercial Pt/C catalyst. In addition, the distinct structure endows the Rh-doped PdCu intermetallics with highly stable ORR durability with unaltered half-wave potential (E_1/2) and mass activity after continuous 20000 cycles, which are higher than those of other electrocatalysts. Furthermore, the E_1/2 of the Rh-doped PdCu intermetallics decreases by only 5 mV after adding 0.5 mol·L^-1 methanol to the electrolyte, while the commercial Pt/C catalyst negatively shifts by 235 mV and a distinct oxidation peak can be observed. The results indicate that the ORR activity of the Rh-doped PdCu intermetallic electrocatalyst can be well maintained even in the presence of poisoning environment. Our results have demonstrated that Rh-doped PdCu NPs with ordered intermetallic structures is a potential electrocatalyst toward the next-generation high-performance DMFCs.     

含氮原子桥联吡咯基稀土金属双核配合物的合成及催化ε-己内酯的开环聚合反应

RE(CH2SiMe3)3(THF)2和1.5 equiv.(C4H3NHCH2)2NCH3(1)反应合成得到含氮原子桥联吡咯基稀土金属双核配合物[η1∶η1∶η1-(C4H3NCH2)2NCH3]RE{μ-η5∶η5∶η1-(C4H3NCH2)2NCH3}RE[η1∶η1∶η1-(C4H3NCH2)2NCH3](THF)[RE=Y(2),Er(3),Yb(4)],所得配合物经过核磁共振、红外和元素分析表征,配合物2和4经单晶X-Ray进一步确认结构.同时研究了稀土配合物作为单一组分催化剂催化ε-内酯的开环聚合反应.     

Catalytic Selective Dihydrosilylation of Internal Alkynes Enabled by Rare‐Earth Ate Complex

Hydrosilylation of alkynes generally yield vinylsilanes, which are inert to the further hydrosilylation because of the steric effects. Reported here is the first successful dihydrosilylation of aryl‐ and silyl‐substituted internal alkynes enabled by a rare‐earth ate complex to yield geminal bis‐ and tris(silanes), respectively. The lanthanum bis(amido) ate complex supported by an ene‐diamido ligand proved to be the ideal catalyst for this unprecedented transformation, while the same series of yttrium and samarium alkyl and samarium bis(amido) ate complexes exhibited poor activity and selectivity, indicating significant effects of the ionic size and ate structure of the rare‐earth catalysts.     

Rare‐Earth Single Erbium Atoms for Enhanced Photocatalytic CO2 Reduction

The solar‐driven photocatalytic reduction of CO₂ (CO₂RR) into chemical fuels is a promising route to enrich energy supplies and mitigate CO₂ emissions. However, low catalytic efficiency and poor selectivity, especially in a pure‐water system, hinder the development of photocatalytic CO₂RR owing to the lack of effective catalysts. Herein, we report a novel atom‐confinement and coordination (ACC) strategy to achieve the synthesis of rare‐earth single erbium (Er) atoms supported on carbon nitride nanotubes (Er₁/CN‐NT) with a tunable dispersion density of single atoms. Er₁/CN‐NT is a highly efficient and robust photocatalyst that exhibits outstanding CO₂RR performance in a pure‐water system. Experimental results and density functional theory calculations reveal the crucial role of single Er atoms in promoting photocatalytic CO₂RR.     

Theoretical analysis of the anisotropy of the magnetization of the Ho^3＋ ion in holmium iron garnet single crystals

The spontaneous magnetization of the Ho^3＋ ion in holmium iron garnet （HoIG） single crystals in the temperature range of 4.2-294K along the directions [111], [110], and [100] are calculated, taking into account the effects of six magnetically inequivalent sites occupied by the Ho^3＋ ions based on the quantum theory. The calculated results show that the magnetization of the Ho^3＋ ion in HoIG is obviously anisotropic. The theoretical results ave in agreement with those of experiments. A primary interpretation of the anisotropy of magnetization of the Ho^3＋ ion in HoIG is put forward.     

Magnetic and Transport Properties of Tm2Co7B3 Compound

Magnetic and transport properties of Tm₂Co₇B₃ compound have been studied. This compound crystallizes in the hexagonal Ce₂Co₇B₃ type structure. The coercivity (H _c) of the compound was determined from hysteresis measurements in fields up to 4 T. The temperature dependence of coercivity has been explained by a thermally activated process of domain wall motion. The resistivity at low temperatures shows a T ² dependence. At higher temperatures the resistivity is not a linear function of temperature, which indicates an electron-phonon interaction in the presence of a small s-d scattering.     

Time-Resolved Vacuum Ultraviolet Spectroscopy of Er<Superscript>3+</Superscript> Ions in the SrF<Subscript>2</Subscript> Crystal

The photoluminescence and photoexcitation spectra as well as the luminescence decay kinetics of Er³⁺ ions in the visible ultraviolet and vacuum ultraviolet (VUV) regions have been studied by the method of low-temperature, time-resolved VUV-spectroscopy on excitation by synchrotron radiation. In the VUV spectral region of the luminescence of SrF₂:1% Er³⁺, the 146.5-nm band with a time of decay of less than 0.6 nsec was revealed together with the well-known emission band at 164.3 nm (decay constant in the microsecond range). Its possible nature is discussed. The specific features of the formation of photoexcitation spectra of the f-f and f-d transitions in the Er³⁺ ion are considered. Competition between the processes of excitation of f-f and d-f luminescence has been revealed. It manifests itself in the inverse relationship of their photoexcitation spectra in a range of energies of incident photons that are close to the position of the 4fⁿ⁻¹5d configuration levels. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 519–523, July–August, 2005.     

突破间接带局限创新Si基激光器

Si基高效发光与受激光发射是Si基光子学突破性发展的关键课题,它的实现对Si基微电子学的发展有深远的重大意义．由于受到天然Si材料间接带能带结构的限制,Si材料的发光效率极低,更谈不上可实现受激光发射,人工改性就成为当代研究、开拓的主要途径．新的Si基直接带体材料(如β-FeSi2等)的探索,Ge／Si量子阱、超晶格、量子点的能带工程介观改性,子带发光跃迁的探索,异类元素插入短周期超晶格中的化学键改性,以及SiO2高浓度nc-Si的生成和高激活度稀土离子的掺入发光等已开展了多途径的研究,不同程度上取得了重要的进展,一种MIS结构电子隧道注入高效发光器件已在SiO2：RE MOS结构中实现．运用激光器件物理的深入设计和新的器件技术的引入,可以预计本世纪初叶,对实现Si基激光器的奢望将会成为现实,无疑它对Si基光子学、Si基集成光电子学乃至信息高科技的发展将作出历史性的巨大贡献．     

Rare-Earth–Transition-Metal Organic–Inorganic Hybrids Based on Keggin-type Polyoxometalates and Pyrazine-2,3-dicarboxylate

Five rare-earth–transition-metal (RE–TM) heterometal organic–inorganic hybrids based on Keggin-type silicotungstates and mixed ligands H2pzda (pzda=pyrazine-2,3-dicarboxylate) and en (en=ethylenediamine) (enH2)[Cu(en)2(H2O)]2{[Cu(en)2][Cu(en)2(H2O)][(α-SiW11 O39)RE(H2O)(pzda)]}2⋅n H2O (n≈4; RE=YIII ( 1 ), DyIII ( 2 ), YbIII ( 3 ), and LuIII ( 4 )) and [Cu(en)2(H2O)]2{[Cu(en)2]2[Cu(pzda)2][(α-H2SiW11O39)Ce(H2O)]2}⋅n H2O ( 5 ; n≈8) have been hydrothermally synthesized and structurally characterized. Compounds 1–5 all contain the dimeric mono-RE substituted Keggin [RE(α-SiW11O39)]210− subunits linked by H2pzda ligands. Interestingly, 1–4 exhibit discrete structures, in which the H2pzda ligand acts as a tetradentate ligand to bind the RE and Cu cations, whereas 5 displays a 1D double-chain architecture, in which the H2pzda ligand adopts a new pentadentate mode to connect the Ce and Cu cations. To our knowledge, 1–5 represent the first monovacant Keggin-type silicotungstates containing both RE–TM heterometals and mixed ligands. The luminescence of 2 is derived from the combination of the DyIII cations and H2pzda ligands, whereas the luminescence properties of 1 and 3–5 are attributable to the H2pzda ligands.