Experimental evidence of new tetragonal polymorphs of silicon formed through ultrafast laser-induced confined microexplosion

Ordinary materials can transform into novel phases at extraordinary high pressure and temperature. The recently developed method of ultrashort laser-induced confined microexplosions initiates a non-equilibrium disordered plasma state. Ultra-high quenching rates overcome kinetic barriers to the formation of new metastable phases, which are preserved in the surrounding pristine crystal for subsequent exploitation. Here we demonstrate that confined microexplosions in silicon produce several metastable end phases. Comparison with an ab initio random structure search reveals six energetically competitive potential phases, four tetragonal and two monoclinic structures. We show the presence of bt8 and st12, which have been predicted theoretically previously, but have not been observed in nature or in laboratory experiments. In addition, the presence of the as yet unidentified silicon phase, Si-VIII and two of our other predicted tetragonal phases are highly likely within laser-affected zones. These findings may pave the way for new materials with novel and exotic properties

Polyoxometalate (POM)-layered double hydroxides (LDH) composite materials: design and catalytic applications

Layered double hydroxides (LDHs) are an important large class of two-dimensional (2D) anionic lamellar materials that possess flexible modular structure, facile exchangeability of inter-lamellar guest anions and uniform distribution of metal cations in the layer. Owing to the modular accessible gallery and unique inter-lamellar chemical environment, polyoxometalates (POMs) intercalated with LDHs has shown a vast array of physical properties with applications in environment, energy, catalysis, etc. Here we describe how polyoxometalate clusters can be used as building components for the construction of systems with important catalytic properties. This review article mainly focuses on the discussion of new synthetic approaches developed recently that allow the incorporation of the element of design in the construction of a fundamentally new class of materials with pre-defined functionalities in catalytic applications. Introducing the element of design and taking control over the finally observed functionality we demonstrate the unique opportunity for engineering materials with modular properties for specific catalytic applications

A Three-Dimensional Dynamic Supramolecular "Sticky Fingers" Organic Framework.

Engineering high-recognition host-guest materials is a burgeoning area in basic and applied research. The challenge of exploring novel porous materials with advanced functionalities prompted us to develop dynamic crystalline structures promoted by soft interactions. The first example of a pure molecular dynamic crystalline framework is demonstrated, which is held together by means of weak "sticky fingers" van der Waals interactions. The presented organic-fullerene-based material exhibits a non-porous dynamic crystalline structure capable of undergoing single-crystal-to-single-crystal reactions. Exposure to hydrazine vapors induces structural and chemical changes that manifest as toposelective hydrogenation of alternating rings on the surface of the [60]fullerene. Control experiments confirm that the same reaction does not occur when performed in solution. Easy-to-detect changes in the macroscopic properties of the sample suggest utility as molecular sensors or energy-storage materials

Continuous-feed nanocasting process for the synthesis of bismuth nanowire composites

We present a novel, continuous-feed nanocasting procedure for the synthesis of bismuth nanowire structures embedded in the pores of a mesoporous silica template. The immobilization of a bismuth salt inside the silica template from a diluted metal salt solution yields a sufficiently high loading to obtain electrically conducting bulk nanowire composite samples after reduction and sintering the nanocomposite powders. Electrical resistivity measurements of sintered bismuth nanowires embedded in the silica template reveal size-quantization effects

Doping and band-gap engineering of an intrazeolite tungsten(VI) oxide supralattice

New results are presented concerning the topotactic self-assembly, n-type doping and band-gap engineering of an intrazeolite tungsten(VI) oxide supralattice n(W03)-Na56Y, where 0 < η < 32, built-up of single size and shape (W03)2 dimers. In particular it has been found that the oxygen content of these dimers can be quantitatively adjusted by means of a thermal vacuum induced reversible reductive-elimination oxidative-addition of dioxygen. This provides access to new n(W03.x)-Na56Y materials (0 < χ ^ 1.0) in which the oxygen content, structural properties and electronic architecture of the dimers are changed. In this way one can precisely control the oxidation state, degree of η-doping and band-filling of a tungsten(VI) oxide supralattice through an approach which can be considered akin to, but distinct in detail to, that found in the Magneli crystallographic shear phases of non-stoichiometric bulk W03.x . Another discovery concerns the ability to alter local electrostatic fields experienced by the tungsten(VI) oxide moieties housed in the 13Ä supercages of 16(W03)-M36Y, by varying the ionic potential of the constituent supercage M + cations across the alkali metal series. This method provides the first opportunity to fine-tune the band-gap of a tungsten(VI) oxide supralattice. Α miniband electronic description is advanced as a qualitative first attempt to understand the origin of the above effects. The implications of these discoveries are that cluster size, composition and intrinsic electrostatic field effects can be used to "chemically manipulate" (engineer) the doping and band architecture of intrazeolite supralattices of possible interest in quantum electronics and nonlinear optics