Single-bond formation and characterization with a scanning tunneling microscope

A scanning tunneling microscope (STM) was used to manipulate the bonding of a carbon monoxide (CO) molecule and to analyze the structure and vibrational properties of individual products. Individual iron (Fe) atoms were evaporated and coadsorbed with CO molecules on a silver (110) surface at 13 kelvin. A CO molecule was transferred from the surface to the STM tip and bonded with an Fe atom to form Fe(CO). A second CO molecule was similarly transferred and bonded with Fe(CO) to form Fe(CO)(2). Controlled bond formation and characterization at the single-bond level probe chemistry at the spatial limit.     

Magnetism from the atom to the bulk in iron, cobalt, and nickel clusters

Molecular beam deflection measurements of small iron, cobalt, and nickel clusters show how magnetism develops as the cluster size is increased from several tens to several hundreds of atoms for temperatures between 80 and 1000 K. Ferromagnetism occurs even for the smallest sizes: for clusters with fewer than about 30 atoms the magnetic moments are atomlike; as the size is increased up to 700 atoms, the magnetic moments approach the bulk limit, with oscillations probably caused by surface-induced spin-density waves. The trends are explained in a magnetic shell model. A crystallographic phase transition from high moment to low moment in iron clusters has also been identified.     

Spin conservation accounts for aluminum cluster anion reactivity pattern with O2

The reactivity pattern of small (approximately 10 to 20 atoms) anionic aluminum clusters with oxygen has posed a long-standing puzzle. Those clusters with an odd number of atoms tend to react much more slowly than their even-numbered counterparts. We used Fourier transform ion cyclotron resonance mass spectrometry to show that spin conservation straightforwardly accounts for this trend. The reaction rate of odd-numbered clusters increased appreciably when singlet oxygen was used in place of ground-state (triplet) oxygen. Conversely, monohydride clusters AlnH-, in which addition of the hydrogen atom shifts the spin state by converting formerly open-shell structures to closed-shell ones (and vice versa), exhibited an opposing trend: The odd-n hydride clusters reacted more rapidly with triplet oxygen. These findings are supported by theoretical simulations and highlight the general importance of spin selection rules in mediating cluster reactivity.     

Nitrogenase MoFe-protein at 1.16 A resolution: a central ligand in the FeMo-cofactor

A high-resolution crystallographic analysis of the nitrogenase MoFe-protein reveals a previously unrecognized ligand coordinated to six iron atoms in the center of the catalytically essential FeMo-cofactor. The electron density for this ligand is masked in structures with resolutions lower than 1.55 angstroms, owing to Fourier series termination ripples from the surrounding iron and sulfur atoms in the cofactor. The central atom completes an approximate tetrahedral coordination for the six iron atoms, instead of the trigonal coordination proposed on the basis of lower resolution structures. The crystallographic refinement at 1.16 angstrom resolution is consistent with this newly detected component being a light element, most plausibly nitrogen. The presence of a nitrogen atom in the cofactor would have important implications for the mechanism of dinitrogen reduction by nitrogenase.     

Removal of meteoric iron on polar mesospheric clouds

Polar mesospheric clouds are thin layers of nanometer-sized ice particles that occur at altitudes between 82 and 87 kilometers in the high-latitude summer mesosphere. These clouds overlap in altitude with the layer of iron (Fe) atoms that is produced by the ablation of meteoroids entering the atmosphere. Simultaneous observations of the Fe layer and the clouds, made by lidar during midsummer at the South Pole, demonstrate that essentially complete removal of Fe atoms can occur inside the clouds. Laboratory experiments and atmospheric modeling show that this phenomenon is explained by the efficient uptake of Fe on the ice particle surface.     

Quantum confinement and host/guest chemistry: probing a new dimension

Nanoparticulate metals and semiconductors that have atomic arrangements at the interface of molecular clusters and "infinite" solid-state arrays of atoms have distinctive properties determined by the extent of confinement of highly delocalized valence electrons. At this interface, the total number of atoms and the geometrical disposition of each atom can be used to significantly modify the electronic and photonic response of the medium. In addition to teh novel inherent physical properties of the quantum-confined moieties, their "packaging" into nanocomposite bulk materials can be used to define the confinement surface states and environment, intercluster interactions, the quantum-confinement geometry, and the effective charge-carrier density of the bulk. Current approaches for generating nanostructures of conducting materials are briefly reviewed, especially the use of three-dimensional crystalline superlattices as hosts for quantum-confined semiconductor atom arrays (such as quantum wires and dots) with controlled inter-quantum-structure tunneling.     

动态条件下壳聚糖稳定纳米铁去除水体中Cr（Ⅵ）的研究

以重金属Cr(Ⅵ)为目标污染物,在两种实验条件下(实验柱Ⅰ为模拟污染水样,实验柱Ⅱ为实际污染水样)考察了壳聚糖稳定纳米铁对Cr(Ⅵ)的去除能力。实验柱Ⅰ和实验柱Ⅱ分别在第160PV和127PV时发生了击穿效应。与实验柱Ⅰ相比,实验柱Ⅱ中壳聚糖稳定纳米铁对Cr(Ⅵ)的去除能力降低了25%。SEM表征显示,实验柱Ⅱ中壳聚糖稳定纳米铁的表面形成了许多葡萄状晶体,它们的存在导致实验柱Ⅱ中纳米铁的去除能力明显低于实验柱Ⅰ。XPS表征显示,由于Ca和Mg的氢氧化物替代了部分铁氢氧化物,导致实验柱Ⅱ中壳聚糖稳定纳米铁表面Fe原子的相对含量低于实验柱I。Cr元素高分辨率XPS能谱分析显示,在实验柱Ⅰ的条件下Cr(Ⅵ)被还原得更充分,而且在两种实验条件下都有部分Cr(Ⅵ)被吸附在纳米铁表面最终没有被零价铁所还原。     

In Situ X-ray Absorption Study of Surface Complexes: Selenium Oxyanions on agr-FeOOH

A novel application of x-ray absorption spectroscopy has provided structural information for ions sorbed at oxide-water interfaces. As an example, in situ extended x-ray absorption fine structure (EXAFS) measurements of adsorbed selenate and selenite ions at ah alpha-FeOOH(goethite)-water interface have been performed; these measurements show that selenate forms a weakly bonded, outer-sphere complex and that selenite forms a strongly bonded, inner-sphere complex. The selenite ion is bonded directly to the goethite surface in a bidentate fashion with two iron atoms 3.38 angstroms from the selenium atom. Adsorbed selenate has no iron atom in the second coordination shell of selenium, which indicates retention of its hydration sphere upon sorption. This method provides direct structural information for adsorbed species at solid-liquid interfaces.     

喷施无机铁对农田人参产量、质量及铁元素质量分数的影响

采用叶面喷施的方法,研究农田人参叶片对不同质量浓度Fe2+的吸收及吸收后的分配规律,以及喷施Fe2+对人参产量和总皂苷质量分数的影响.结果表明:农田人参叶片可有效吸收叶面供给的铁营养,并且吸收后可向根部运输,随着铁元素质量浓度的升高,人参叶片吸收铁元素的量增加,向根部运输铁元素的量也随之增加.喷施低质量浓度Fe2+ (...     

N₂reduction and hydrogenation to ammonia by a molecular iron-potassium complex

The most common catalyst in the Haber-Bosch process for the hydrogenation of dinitrogen (N(2)) to ammonia (NH(3)) is an iron surface promoted with potassium cations (K(+)), but soluble iron complexes have neither reduced the N-N bond of N(2) to nitride (N(3-)) nor produced large amounts of NH(3) from N(2). We report a molecular iron complex that reacts with N(2) and a potassium reductant to give a complex with two nitrides, which are bound to iron and potassium cations. The product has a Fe(3)N(2) core, implying that three iron atoms cooperate to break the N-N triple bond through a six-electron reduction. The nitride complex reacts with acid and with H(2) to give substantial yields of N(2)-derived ammonia. These reactions, although not yet catalytic, give structural and spectroscopic insight into N(2) cleavage and N-H bond-forming reactions of iron.     

Covalent Group IV Atomic Clusters

Atomic clusters containing from two to several hundred atoms offer the possibility of studying the transition from molecules to crystalline solids. The covalent group IV elements carbon, silicon, and germanium are now being examined with this long-range objective. These elements are particularly interesting because of the very different character of their crystalline solids and because they are intermediate between metals and insulators in the nature of their bonding. Small mass-selected atom cluster ions are formed by pulsed laser techniques and identified by time-of-flight methods. Laser photoexcitation is used to study the relative stability of these clusters and their modes of fragmentation. These modes for C(n)(+) clusters, which tend to fragment with a characteristic loss of a neutral C(3), are found to be different from the modes for Si(n)(+) and Ge(n)(+) clusters, which tend to fragment to "magic" clusters such as Si(4)(+), Si(6)(+) and Si(10)(+). These experimental results can be accounted for by recent theoretical calculations of the ground-state structure and stability of small silicon and carbon clusters. Several theoretical approaches give consistent results, showing that small silicon clusters are compact and different from small fragments of the bulk crystal. Calculations show that carbon clusters change from linear structures toward cyclic structures as the cluster size increases, but with significant odd-even differences.     

Field-Induced Nanometer- to Atomic-Scale Manipulation of Silicon Surfaces with the STM

The controlled manipulation of silicon at the nanometer scale will facilitate the fabrication of new types of electronic devices. The scanning tunneling microscope (STM) can be used to manipulate strongly bound silicon atoms or clusters at room temperature. Specifically, by using a combination of electrostatic and chemical forces, surface atoms can be removed and deposited on the STM tip. The tip can then move to a predetermined surface site, and the atom or cluster can be redeposited. The magnitude of such forces and the amount of material removed can be controlled by applying voltage pulses at different tip-surface separations.     

Identification of active gold nanoclusters on iron oxide supports for CO oxidation

Gold nanocrystals absorbed on metal oxides have exceptional properties in oxidation catalysis, including the oxidation of carbon monoxide at ambient temperatures, but the identification of the active catalytic gold species among the many present on real catalysts is challenging. We have used aberration-corrected scanning transmission electron microscopy to analyze several iron oxide-supported catalyst samples, ranging from those with little or no activity to others with high activities. High catalytic activity for carbon monoxide oxidation is correlated with the presence of bilayer clusters that are approximately 0.5 nanometer in diameter and contain only approximately 10 gold atoms. The activity of these bilayer clusters is consistent with that demonstrated previously with the use of model catalyst systems.     

X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor

Nitrogenase is a complex enzyme that catalyzes the reduction of dinitrogen to ammonia. Despite insight from structural and biochemical studies, its structure and mechanism await full characterization. An iron-molybdenum cofactor (FeMoco) is thought to be the site of dinitrogen reduction, but the identity of a central atom in this cofactor remains unknown. Fe Kβ x-ray emission spectroscopy (XES) of intact nitrogenase MoFe protein, isolated FeMoco, and the FeMoco-deficient nifB protein indicates that among the candidate atoms oxygen, nitrogen, and carbon, it is carbon that best fits the XES data. The experimental XES is supported by computational efforts, which show that oxidation and spin states do not affect the assignment of the central atom to C(4-). Identification of the central atom will drive further studies on its role in catalysis.     

火焰原子吸收光谱法测定婴幼儿奶粉中铁、锌元素含量

[目的]鉴于婴幼儿食品的特殊性和重要性,对婴幼儿配方奶粉中的铁、锌元素含量进行测定。[方法]采用干法灰化法处理6种婴幼儿配方奶粉,探究适合奶粉灰化的温度,并且用火焰原子吸收光谱法测定奶粉中铁、锌元素的含量。[结果]试验表明,测定铁、锌元素含量时奶粉的灰化温度为450～500℃;同一厂家生产的同一品牌不同成长阶段的婴幼儿配方奶粉,铁含量存在一定的差异,锌含量存在显著性差异,同一厂家生产的不同品牌的婴儿(较大婴儿)配方奶粉,铁、锌含量均不存在显著性差异,不同品牌幼儿配方奶粉的铁、锌含量存在显著性差异;6种奶粉的铁、锌元素含量均符合国家标准GB/T5413.21-1997。[结论]科学全面地评价婴幼儿配方奶粉中铁和锌元素的含量,对评价奶粉的品质以及正确引导消费者消费具有积极的现实意义。     

液态Ca50Zn50合金快速凝固过程中微观结构的演变特性

采用分子动力学方法对液态Ca50Zn50合金的快速凝固过程进行了模拟研究.并采用双体分布函数、HA键型指数法、原子团类型指数法(CTIM)和可视化等方法对凝固过程中微观结构的演变特性进行了分析.结果表明：由于Ca,Zn原子的半径差异较大,导致总双体分布函数的第1峰明显分裂成为3个次峰,随着温度下降,半径较小的Zn原子互为近邻的几率明显增加.系统中1551键型所构成的二十面体基本原子团(12 0 12 0)的数量占绝对优势,对非晶态结构的形成起主导作用.系统中基本原子团的中心原子主要是原子半径较小的Zn原子.具有短程序的基本原子团之间大多以共顶点(VS),共棱线(ES),共面(FS)和相互交叉(IS)的方式相结合,在凝固形成非晶态的过程中,基本原子团大多以相互交叉(IS)的方式相结合,最后形成各种不同尺寸的、原子结合比较紧密、结构比较稳定的较大团簇.     

Quantum phase interference and parity effects in magnetic molecular clusters

An experimental method based on the Landau-Zener model was developed to measure very small tunnel splittings in molecular clusters of eight iron atoms, which at low temperature behave like a nanomagnet with a spin ground state of S = 10. The observed oscillations of the tunnel splittings as a function of the magnetic field applied along the hard anisotropy axis are due to topological quantum interference of two tunnel paths of opposite windings. Transitions between quantum numbers M = -S and (S - n), with n even or odd, revealed a parity effect that is analogous to the suppression of tunneling predicted for half-integer spins. This observation is direct evidence of the topological part of the quantum spin phase (Berry phase) in a magnetic system.     

Effect of Pressure on the Composition of the Lower Mantle End Member FexO

The composition limits of Fe(x)O are sensitive to both pressure and temperature. Earlier studies have shown that Fe(x)O becomes highly nonstoichiometric when in equilibrium with metallic iron above 10 gigapascals, which is difficult to reconcile with available thermodynamic data. Experiments with a uniaxial split-sphere apparatus demonstrate that the iron content of Fe(x)O increases continuously at high pressure in excellent agreement with quantitative models and suggest that there is a discontinuity in the elastic properties of Fe(x)O above x = 0.95. On the basis of these results, it is inferred that the Earth's present lower mantle is not in equilibrium with metallic iron.     

Is soot composed predominantly of carbon clusters?

Soot generated from diesel fuel in a combustion tube is characterized by microanalysis, x-ray diffraction, chemical reactivity, and nuclear magnetic resonance to address the recent proposal of the significance of carbon clusters in soot. The data support a traditional model of soot as polynuclear aromatic compounds rather than as clusters of carbon atoms with minimal edge site density. The amounts of noncarbon atoms in the soot (hydrogen, oxygen, nitrogen, and sulfur) are commensurate with the edge density of the crystallites (2 by 2 nanometers) inferred from diffraction. The chemistry of soot, in being reduced by potassium metal and alkylated by alkyl iodides, is that known for aromatic compounds and not that anticipated for materials such as graphite, with a small fraction of carbon atoms on edges.     

Off-Resonance Conduction Through Atomic Wires

The electrical resistance of wires consisting of either a single xenon atom or two xenon atoms in series was measured and calculated on the basis of an atom-jellium model. Both the measurement and the calculation yielded a resistance of 10(5) ohms for the single-xenon atom system and 10(7) ohms for the two-xenon atom system. These resistances greatly exceeded the 12,900-ohm resistance of an ideal one-dimensional conduction channel because conduction through the xenon atoms occurs through the tail of the xenon 6s resonance, which lies far above the Fermi level. This conduction process in an atom-sized system can now be understood in terms of the electronic states of individual atoms.