Green nanochemistry: metal oxide nanoparticles and porous thin films from bare metal powders.

A universal, simple, robust, widely applicable and cost-effective aqueous process is described for a controlled oxidative dissolution process of micrometer-sized metal powders to form high-purity aqueous dispersions of colloidally stable 3-8 nm metal oxide nanoparticles. Their utilization for making single and multilayer optically transparent high-surface-area nanoporous films is demonstrated. This facile synthesis is anticipated to find numerous applications in materials science, engineering, and nanomedicine.

Spatially confined redox chemistry in periodic mesoporous hydridosilica-nanosilver grown in reducing nanopores.

Periodic mesoporous hydridosilica, PMHS, is shown for the first time to function as both a host and a mild reducing agent toward noble metal ions. In this archetypical study, PMHS microspheres react with aqueous Ag(I) solutions to form Ag(0) nanoparticles housed in different pore locations of the mesostructure. The dominant reductive nucleation and growth process involves SiH groups located within the pore walls and yields molecular scale Ag(0) nanoclusters trapped and stabilized in the pore walls of the PMHS microspheres that emit orange-red photoluminescence. Lesser processes initiated with pore surface SiH groups produce some larger spherical and worm-shaped Ag(0) nanoparticles within the pore voids and on the outer surfaces of the PMHS microspheres. The intrinsic reducing power demonstrated in this work for the pore walls of PMHS speaks well for a new genre of chemistry that benefits from the mesoscopic confinement of Si-H groups.

Nanocrystal self-assembly with rod-rod block copolymers.

Two distinct morphologies of hexylselenophene-hexylthiophene rod-rod block copolymer films can be prepared depending on the molecular weight of the sample (see picture: left M(n) =12.9, right M(n) =3.9 kg mol(-1)). These polymers can be used to organize spherical CdSe nanocrystals (yellow) into either dispersed or aligned hierarchical structures. Scale bars: 200 nm.

Ultrathin Bi2S3 nanowires: surface and core structure at the cluster-nanocrystal transition.

Herein, we present the structural characterization of the core and surface of colloidally stable ultrathin bismuth sulfide (Bi(2)S(3)) nanowires using X-ray Absorption Spectroscopy (EXAFS and XANES), X-ray Photoelectron Spectroscopy (XPS), and Nuclear Magnetic Resonance (NMR). These three techniques allowed the conclusive structural characterization of the inorganic core as well as the coordination chemistry of the surface ligands of these structures, despite the absence of significant translational periodicity dictated by their ultrathin diameter (1.6 nm) and their polycrystallinity. The atomic structure of the inorganic core is analogous to bulk bismuthinite, but Bi atoms display a remarkably higher coordination number than in the bulk. This can be only explained by a model in which each bismuth atom at the surface (or in close proximity to it) is bound to at least one ligand at any time.

Cross-linking Bi2S3 ultrathin nanowires: a platform for nanostructure formation and biomolecule detection.

This paper describes the use of chemical cross-linking of ultrathin inorganic nanowires as a bottom-up strategy for nanostructure fabrication as well as a chemical detection platform. Nanowire microfibers are produced by spinning a nanowire dispersion into a cross-linker solution at room temperature. Nanomembranes with thicknesses down to 50 nm were obtained by injecting the nanowire dispersion at the cross-linker-solution/air interface. Furthermore, the sensitivity of the nanowire to amine cross-linkers allowed development of a novel sensing platform for small molecules, like the neurotransmitter serotonin, with detection limits in the picomolar regime.

Towards flexible inorganic "mesomaterials": one-pot low temperature synthesis of mesostructured nanocrystalline titania.

We hereby report a simple route for the low temperature synthesis of mesoporous nanocrystalline titania involving brief hydrothermal treatment of butanolic precursors and non-ionic tri-block-copolymer surfactant at 100 degrees C, followed by evaporation induced self assembly to make a crack-free flexible film. At no time in the film-forming process is a temperature of more than 120 degrees C reached, thereby permitting the use of substrates that are not stable to higher temperatures.

Synthesis and Crystal Structure of δ-GeS2 , the First Germanium Sulfide with an Expanded Framework Structure.

Polycondensation of molecular adamantanoid [Ge4 S10 ]4- precursors at a remarkably low temperature (50°C) affords the crystalline binary dichalcogenide δ-GeS2 . Its crystal structure contains two interpenetrating cristobalite-like frameworks composed of adamantanoid [Ge4 S6 S4/2 ] building blocks. Rings containing 24 atoms form the largest pores of each network (shown on the right).

Nanoparticle films and photonic crystal multilayers from colloidally stable, size-controllable zinc and iron oxide nanoparticles.

We report a facile sol-gel synthesis of colloidally stable Fe(2)O(3) and ZnO nanoparticles in alcoholic solvents, ROH, where R = methyl, ethyl, n-propyl, isopropyl, and tert-butyl. We show that nanoparticles of ZnO (4-42) nm and Fe(2)O(3) (4-38 nm) monotonically increase in size upon increasing the alkyl chain length and branching of the alcohol solvent. These colloidally stable and size-controllable metal oxide nanoparticles enable the formation of high optical quality films and photonic crystal multilayers whose component layer thickness, refractive index, porosity, and surface area are found to scale with the nature of the alcohol. Utility of these colloidally stable nanoparticles is demonstrated by preparation of one-dimensional porous photonic crystals comprising ncZnO/ncWO(3) and ncFe(2)O(3)/ncWO(3) multilayers whose photonic stop band can be tuned by tailoring nanoparticle size. Myriad applications can be envisaged for these nanoparticle films in, for example, heterogeneous catalysis, photocatalysis, electrocatalysis, chemical sensors, and solar cells.

Flash nano-welding: investigation and control of the photothermal response of ultrathin bismuth sulfide nanowire films.

Ultrathin Bi2S3 nanowires undergo a pronounced photothermal response to irradiation from a commercial camera flash. Controlled nano-welding was shown by using single walled carbon nanotube mats as an electrically and thermally conductive substrate. The resulting welded nanowire film is denser and has significantly lower resistance than unflashed bilayer films.

Bulk microphase segregation of an asymmetric organometallic-inorganic diblock copolymer: a remarkable example of concentric cylinders.

We report that an asymmetric diblock copolymer, poly(ferrocenyldimethylsilane-b-dimethylsiloxane) (PFS90-b-PDMS900, PDI = 1.01, volume fraction PFS = 0.20), self-assembles in the bulk state to form a hexagonal periodic structure with a remarkable morphology. Part of the major component forms the core of concentric cylinders with a mean diameter of 35.5 nm surrounded by a 7 nm thick shell of PFS. The remaining PDMS fills the interstitial spaces. The morphology was elucidated by small-angle X-ray scattering, as well as by scanning and conventional transmission electron microscopy.

Lanthanum strontium manganite/yttria-stabilized zirconia nanocomposites derived from a surfactant assisted, co-assembled mesoporous phase.

A one-pot, soft-chemistry, surfactant-assisted co-assembly approach to prepare La(1-x)Sr(x)MnO(3) (LSM)/Y(2)O(3)-stabilized ZrO(2) (YSZ) nanocomposites for use as solid oxide fuel cell (SOFC) cathodes has been investigated. This material with sub-hundred nanometer grain sizes for each phase is the first such nanocomposite where aqueous-based precursors of each component are incorporated in a single synthetic step. This approach utilizes the co-assembly of an anionic yttrium/zirconium acetatoglycolate gel, cetyltrimethylammonium bromide as the cationic surfactant template, and inorganic La, Mn, and Sr salts under alkaline aqueous conditions. The resulting as-synthesized product is an amorphous mesostructured organic/inorganic composite, which is transformed to a mesoporous inorganic oxide with nanocrystalline YSZ walls upon calcination. Calcination to temperatures above 600 degrees C lead to collapse of the mesopores followed by further crystallization of the nanocrystalline YSZ phase and a final crystallization of the LSM perovskite phase above 1000 degrees C. Both the fully crystalline LSM/YSZ and the mesoporous intermediate phase have been investigated for phase homogeneity by TEM energy-dispersive X-ray spectroscopy (EDX) mapping and spot analysis which confirm the dispersion of LSM within a YSZ matrix at the nanometer scale. Impedance spectroscopy analysis of LSM/YSZ nanocomposite electrodes demonstrate a low polarization resistance of around 0.2 omega cm(2) with an activation energy (E(a)) as low as 1.42 eV. Cathodic polarization studies show stable current densities over a 40 h test demonstration.