Tunable quasi-two-dimensional electron gases in oxide heterostructures

We report on a large electric-field response of quasi-two-dimensional electron gases generated at interfaces in epitaxial heterostructures grown from insulating oxides. These device structures are characterized by doping layers that are spatially separated from high-mobility quasi-two-dimensional electron gases and therefore present an oxide analog to semiconducting high-electron mobility transistors. By applying a gate voltage, the conductivity of the electron gases can be modulated through a quantum phase transition from an insulating to a metallic state.     

Single-crystal nanorings formed by epitaxial self-coiling of polar nanobelts

Freestanding single-crystal complete nanorings of zinc oxide were formed via a spontaneous self-coiling process during the growth of polar nanobelts. The nanoring appeared to be initiated by circular folding of a nanobelt, caused by long-range electrostatic interaction. Coaxial and uniradial loop-by-loop winding of the nanobelt formed a complete ring. Short-range chemical bonding among the loops resulted in a single-crystal structure. The self-coiling is likely to be driven by minimizing the energy contributed by polar charges, surface area, and elastic deformation. Zinc oxide nanorings formed by self-coiling of nanobelts may be useful for investigating polar surface-induced growth processes, fundamental physics phenomena, and nanoscale devices.     

Ferroelectricity at the nanoscale: local polarization in oxide thin films and heterostructures

Ferroelectric oxide materials have offered a tantalizing potential for applications since the discovery of ferroelectric perovskites more than 50 years ago. Their switchable electric polarization is ideal for use in devices for memory storage and integrated microelectronics, but progress has long been hampered by difficulties in materials processing. Recent breakthroughs in the synthesis of complex oxides have brought the field to an entirely new level, in which complex artificial oxide structures can be realized with an atomic-level precision comparable to that well known for semiconductor heterostructures. Not only can the necessary high-quality ferroelectric films now be grown for new device capabilities, but ferroelectrics can be combined with other functional oxides, such as high-temperature superconductors and magnetic oxides, to create multifunctional materials and devices. Moreover, the shrinking of the relevant lengths to the nanoscale produces new physical phenomena. Real-space characterization and manipulation of the structure and properties at atomic scales involves new kinds of local probes and a key role for first-principles theory.     

铜陵铜尾矿废弃地中氧化铁研究

[目的]对铜尾矿废弃地中的氧化铁进行研究,探讨不同类型氧化铁对土壤形成过程的影响。[方法]以铜陵2处不同时间弃置的铜尾矿废弃地为对象,采用化学分析法研究了自然生态恢复过程中3类铁氧化物（无定形氧化铁、游离氧化铁和络合态氧化铁）的含量。[结果1尾矿废弃物无定形氧化铁含量为（1．73±0．77）～（9．68±2．94）g/kg,氧化铁活化度为（4．80±3．85）％-（91．94±4．34）％;游离氧化铁、晶质态氧化铁含量和游离度分别为（9．10±1．57）～（42．77±12．69）、（2．50±0．57）～（42．05±13．46）g／kg和（8．17±1．77）％～（20．02．±5．38）％;成土时间较短的杨山冲铜尾矿废弃地不同发育层尾矿中3种氧化铁含量差异较小,而弃置时间较长的铜官山尾矿废弃地随深度增加无定形氧化铁逐渐降低,游离氧化铁和络合态氧化铁逐渐增加。相关分析表明：2处尾矿废弃地pH值与无定形氧化铁含量及氧化铁活化度呈极显著正相关．而与游离氧化铁含量、铁游离度、晶质态氧化铁含量和络合态氧化铁含量呈极显著负相关;有机质含量与无定形氧化铁含量和氧化铁活化度呈极显著负相关,而与游离氧化铁含量、游离度及晶质态氧化铁含量呈极显著正相关.目前,铜陵铜尾矿废弃地尚处于成土过程的初期阶段,大量问题仍有待于进一步研究。[结论]探索了自然生态恢复过程中尾矿废弃地中铁氧化物的形态、含量变化特征及其影响因素,为进一步揭示铜尾矿及类似尾矿废弃物的成土过程、成土机制等理论研究提供参考。     

Piezoelectric nanogenerators based on zinc oxide nanowire arrays

We have converted nanoscale mechanical energy into electrical energy by means of piezoelectric zinc oxide nanowire (NW) arrays. The aligned NWs are deflected with a conductive atomic force microscope tip in contact mode. The coupling of piezoelectric and semiconducting properties in zinc oxide creates a strain field and charge separation across the NW as a result of its bending. The rectifying characteristic of the Schottky barrier formed between the metal tip and the NW leads to electrical current generation. The efficiency of the NW-based piezoelectric power generator is estimated to be 17 to 30%. This approach has the potential of converting mechanical, vibrational, and/or hydraulic energy into electricity for powering nanodevices.     

Complexity in strongly correlated electronic systems

A wide variety of experimental results and theoretical investigations in recent years have convincingly demonstrated that several transition metal oxides and other materials have dominant states that are not spatially homogeneous. This occurs in cases in which several physical interactions-spin, charge, lattice, and/or orbital-are simultaneously active. This phenomenon causes interesting effects, such as colossal magnetoresistance, and it also appears crucial to understand the high-temperature superconductors. The spontaneous emergence of electronic nanometer-scale structures in transition metal oxides, and the existence of many competing states, are properties often associated with complex matter where nonlinearities dominate, such as soft materials and biological systems. This electronic complexity could have potential consequences for applications of correlated electronic materials, because not only charge (semiconducting electronic), or charge and spin (spintronics) are of relevance, but in addition the lattice and orbital degrees of freedom are active, leading to giant responses to small perturbations. Moreover, several metallic and insulating phases compete, increasing the potential for novel behavior.     

奥地利Wallersee沉积物-水界面铁锰的循环和迁移特征

对奥地利Wallersee沉积物中铁、锰的分布特征进行了分析，说明Wallersee沉积物中铁的循环比锰微弱，铁氧化物的还原作用受到了溶解氧和锰氧化物的双重控制。输入沉积物中的铁大部分都保存于沉积物中。锰氧化物的还原虽然也受到溶解氧的制约，但其还原作用仍比较激烈，孔隙水中有特征的还原峰，只不过峰位下移，所以铁对环境的敏感程度比锰高，沉积物中的铁具有环境记录意义，而锰不具有环境记录意义。铁氧化物中无定形铁氧化物优先还原，晶体铁氧化物可以向无定形铁氧化物转化，参与各种反应。     

Nanophase transition metal oxides show large thermodynamically driven shifts in oxidation-reduction equilibria

Knowing the thermodynamic stability of transition metal oxide nanoparticles is important for understanding and controlling their role in a variety of industrial and environmental systems. Using calorimetric data on surface energies for cobalt, iron, manganese, and nickel oxide systems, we show that surface energy strongly influences their redox equilibria and phase stability. Spinels (M(3)O(4)) commonly have lower surface energies than metals (M), rocksalt oxides (MO), and trivalent oxides (M(2)O(3)) of the same metal; thus, the contraction of the stability field of the divalent oxide and expansion of the spinel field appear to be general phenomena. Using tabulated thermodynamic data for bulk phases to calculate redox phase equilibria at the nanoscale can lead to errors of several orders of magnitude in oxygen fugacity and of 100 to 200 kelvin in temperature.     

铁氧化物-硅酸盐复合物的形成、性质及其对砷的固定

铁氧化物与硅酸盐矿物是土壤中最重要、最活跃的固相组分,它们之间的交互作用直接影响土壤物理化学特性,可有效地调控土壤(类)重金属的迁移、转化。本文以铁氧化物和硅酸盐矿物胶结过程中的一些表观特征变化为出发点,从宏观、表观到微观综述了二者交互作用的界面特性和机理、交互作用前后对土壤砷的固定与释放机制等内容。本文阐明层状硅酸盐与铁氧化物通过多种化学作用而发生表面复合,其中静电作用是作用力之一,带负电荷的硅酸盐与带正电荷的铁氧化物在静电引力的作用下迅速结合,在胶体表面双电层上形成二元团聚体;形成的二元团聚体可改变土壤矿物的表面积和孔性结构、表面电化学特性和物理性质。同时,铁氧化物-硅酸盐复合物表面的活性基团可以通过内层络合共氧的方式将土壤中AsO_4~(2-)络合,形成单核或双核表面络合物而固定砷。复合物对AsO_4~(2-)的吸附能力介于铁氧化物和硅酸盐矿物之间,并更接近铁氧化物的表面吸附特性。本文旨在为土壤砷的原位固定提供理论支撑。     

Size-driven structural and thermodynamic complexity in iron oxides

Iron oxides occur ubiquitously in environmental, geological, planetary, and technological settings. They exist in a rich variety of structures and hydration states. They are commonly fine-grained (nanophase) and poorly crystalline. This review summarizes recently measured thermodynamic data on their formation and surface energies. These data are essential for calculating the thermodynamic stability fields of the various iron oxide and oxyhydroxide phases and understanding their occurrence in natural and anthropogenic environments. The competition between surface enthalpy and the energetics of phase transformation leads to the general conclusion that polymorphs metastable as micrometer-sized or larger crystals can often be thermodynamically stabilized at the nanoscale. Such size-driven crossovers in stability help to explain patterns of occurrence of different iron oxides in nature.     

不同耕作制度和地下水位对水田土壤有机质及氧化铁含量的影响

连续四年在水泥模拟池内进行了不同耕作制度、不同地下水位和不同施肥制度,对土壤有机质和氧化铁含量影响的研究。结果表明:不论何种处理,水田土壤有机质均有所增加,不同耕作制度,以冬泡区土壤的有机质增加最多,但只施化肥进行冬泡的有机质量增加极少,并且第四年开始降低。施用常量有机肥的土壤有机质含量是:高水位区>低水位区;而不同地下水位对施用高量有机肥的土壤有机质含量影响不大。各处理土壤中的无定形氧化铁含量及其活化度均逐年有所增加。无定形氧化铁的含量一般是:耕层>下层,冬泡区>冬作区,高量区>常量区>化肥区。耕层无定形氧化铁含量主要决定于水分和有机质含量,下层则主要受地下水位高低的影响。无定形氧化铁含量与有机质含量之间有一定的相关性。活化度及其变化规律与无定形氧化铁的状况相似。     

Structure of the ultrathin aluminum oxide film on NiAl(110)

The well-ordered aluminum oxide film formed by oxidation of the NiAl(110) surface is the most intensely studied metal surface oxide, but its structure was previously unknown. We determined the structure by extensive ab initio modeling and scanning tunneling microscopy experiments. Because the topmost aluminum atoms are pyramidally and tetrahedrally coordinated, the surface is different from all Al2O3 bulk phases. The film is a wide-gap insulator, although the overall stoichiometry of the film is not Al2O3 but Al10O13. We propose that the same building blocks can be found on the surfaces of bulk oxides, such as the reduced corundum (0001) surface.     

Solution structure of the integral human membrane protein VDAC-1 in detergent micelles

The voltage-dependent anion channel (VDAC) mediates trafficking of small molecules and ions across the eukaryotic outer mitochondrial membrane. VDAC also interacts with antiapoptotic proteins from the Bcl-2 family, and this interaction inhibits release of apoptogenic proteins from the mitochondrion. We present the nuclear magnetic resonance (NMR) solution structure of recombinant human VDAC-1 reconstituted in detergent micelles. It forms a 19-stranded beta barrel with the first and last strand parallel. The hydrophobic outside perimeter of the barrel is covered by detergent molecules in a beltlike fashion. In the presence of cholesterol, recombinant VDAC-1 can form voltage-gated channels in phospholipid bilayers similar to those of the native protein. NMR measurements revealed the binding sites of VDAC-1 for the Bcl-2 protein Bcl-x(L), for reduced beta-nicotinamide adenine dinucleotide, and for cholesterol. Bcl-x(L) interacts with the VDAC barrel laterally at strands 17 and 18.     

Efficient tandem polymer solar cells fabricated by all-solution processing

Tandem solar cells, in which two solar cells with different absorption characteristics are linked to use a wider range of the solar spectrum, were fabricated with each layer processed from solution with the use of bulk heterojunction materials comprising semiconducting polymers and fullerene derivatives. A transparent titanium oxide (TiO(x)) layer separates and connects the front cell and the back cell. The TiO(x) layer serves as an electron transport and collecting layer for the first cell and as a stable foundation that enables the fabrication of the second cell to complete the tandem cell architecture. We use an inverted structure with the low band-gap polymer-fullerene composite as the charge-separating layer in the front cell and the high band-gap polymer composite as that in the back cell. Power-conversion efficiencies of more than 6% were achieved at illuminations of 200 milliwatts per square centimeter.     

福建若干山地土壤不同形态氧化铁的主组元分析

研究福建4条代表性山地土壤垂直带谱中铁的形态的结果表明,氧化铁的活化度和游离度随海拔升高而呈现规律性的变化,应用主组元分析法,前两个主组元全铁和游离铁的累计贡献率已达85％以上。据此认为,氧化铁的活化度可以作为划分常湿润铁铝土亚纲和湿润铁铝土亚纲的一项参考依据。     

A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles

The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.     

含硼氧化物对根际土壤性质和油菜根系形态的影响

通过根箱试验,将含硼氧化物加入到黄棕壤中,观察它们对根际土壤性质的影响。结果表明,含硼氧化物的加入对土壤酸度起到改善作用,提高了土壤pH值,降低了土壤中交换性酸含量。与对照相比,含硼针铁矿提高了土壤中交换性钾、钙、镁的含量。其中,交换性酸、交换性钙和交换性镁的含量均表现出正根际效应,而根际土壤pH值和交换性钾的含量却比非根际低。通过WinRHIZO 2.0根系扫描仪对油菜根系形态进行了分析,结果发现,含硼氧化物的加入使油菜根长、根尖数、根体积以及根表面积增加,促进了油菜根系的生长。     

几种可变电荷土壤中氧化铁类型与磷吸附特性

应用Ｘ射线衍射和化学分析等手段研究了红壤，砖红壤和黄棕壤中氧化铁类型及其与磷吸附和解吸的关系。结果表明：（１）黄棕壤中的氧化铁是针铁矿型，砖红壤和红壤是以赤铁矿为主，棕红壤是以针铁矿为主的针－赤混合型。（２）针铁矿的ＭＣＤ值一般小于赤铁矿的ＭＣＤ值，前者的比表面积大，后者的小。砖红壤中的赤铁矿晶体薄，红壤中的原。（３）针铁矿型氧化铁的磷吸附量明显高于针－赤混合型氧化铁的磷吸附量，并随粘粒中Ｇ／Ｇ（     

土壤和土壤矿物对氯磺隆的吸附

用批量法研究了人工合成的铁、铝氧化物以及砂页岩发育的红壤对氯磺隆的吸附。结果表明: 1)在相同的条件下,氯磺隆在铁、铝氧化物和砂页岩发育的红壤中的吸附量随其浓度的升高而增加,氯磺隆吸附量的顺序为:铁氧化物<铝氧化物<红壤; 2)氯磺隆在铁、铝氧化物和砂页岩发育的红壤中吸附量随pH值的升高而减小。这些情况均与矿物及其组成有关。     

Linked reactivity at mineral-water interfaces through bulk crystal conduction

The semiconducting properties of a wide range of minerals are often ignored in the study of their interfacial geochemical behavior. We show that surface-specific charge density accumulation reactions combined with bulk charge carrier diffusivity create conditions under which interfacial electron transfer reactions at one surface couple with those at another via current flow through the crystal bulk. Specifically, we observed that a chemically induced surface potential gradient across hematite (alpha-Fe2O3) crystals is sufficiently high and the bulk electrical resistivity sufficiently low that dissolution of edge surfaces is linked to simultaneous growth of the crystallographically distinct (001) basal plane. The apparent importance of bulk crystal conduction is likely to be generalizable to a host of naturally abundant semiconducting minerals playing varied key roles in soils, sediments, and the atmosphere.