Josef Breu

Single Nanocrystals of Platinum Prepared by Partial Dissolution of Au-Pt Nanoalloys

Small metal nanoparticles that are also highly crystalline have the potential for showing enhanced catalytic activity. We describe the preparation of single nanocrystals of platinum that are 2 to 3 nanometers in diameter. These particles were generated and immobilized on spherical polyelectrolyte brushes consisting of a polystyrene core (diameter of ∼100 nanometers) onto which long chains of a cationic polyelectrolyte were affixed. In a first step, a nanoalloy of gold and platinum (a solid solution) was generated within the layer of cationic polyelectrolyte chains. In a second step, the gold was slowly and selectively dissolved by cyanide ions in the presence of oxygen. Cryogenic transmission electron microscopy, wide-angle x-ray scattering, and high-resolution transmission electron microscopy showed that the resulting platinum nanoparticles are faceted single crystals that remain embedded in the polyelectrolyte-chain layer. The composite systems of the core particles and the platinum single nanocrystals exhibit an excellent colloidal stability, as well as high catalytic activity in hydrogenation reactions in the aqueous phase.

Clay-Based Nanocomposite Coating for Flexible Optoelectronics Applying Commercial Polymers

Transparency, flexibility, and especially ultralow oxygen (OTR) and water vapor (WVTR) transmission rates are the key issues to be addressed for packaging of flexible organic photovoltaics and organic light-emitting diodes. Concomitant optimization of all essential features is still a big challenge. Here we present a thin (1.5 μm), highly transparent, and at the same time flexible nanocomposite coating with an exceptionally low OTR and WVTR (1.0 × 10(-2) cm(3) m(-2) day(-1) bar(-1) and <0.05 g m(-2) day(-1) at 50% RH, respectively). A commercially available polyurethane (Desmodur N 3600 and Desmophen 670 BA, Bayer MaterialScience AG) was filled with a delaminated synthetic layered silicate exhibiting huge aspect ratios of about 25,000. Functional films were prepared by simple doctor-blading a suspension of the matrix and the organophilized clay. This preparation procedure is technically benign, is easy to scale up, and may readily be applied for encapsulation of sensitive flexible electronics.

Completely Miscible Polyethylene Nanocomposites

A route to fully miscible polyethylene (PE) nanocomposites has been established based on polymer-brush-coated nanoparticles. These nanoparticles can be mixed with PE at any ratio, with homogeneous dispersion, and without aggregation. This allowed a first systematic study of the thermomechanical properties of PE nanocomposites without interference from aggregation effects. We observe that the storage modulus in the semicrystalline state and the softening temperature increase significantly with increasing nanoparticle content, whereas the melt viscosity is unaltered by the presence of nanoparticles. We show that the complete miscibility with the semicrystalline polymer matrix and the improvement of thermomechanical properties in the solid state is caused by the PE-coated nanoparticles being nucleating agents for the crystallization of PE. This provides a general route to fully miscibility nanocomposites with semicrystalline polymers.

Tailoring Shear-Stiff, Mica-like Nanoplatelets

This work introduces a novel facile method to produce shear-stiff, mica-like nanoplatelets by efficient exfoliation. The essence of this procedure is the nonreversible alteration of the interlamellar reactivity of a synthetic fluorohectorite by simple cation exchange. The possibility of switching from highly hydrated to collapsed interlayers permits a highly efficient exfoliation in the swollen state while providing shear-stiffness in the collapsed state. This method restricts cation exchange in the mica-like nanoplatelets to the outer surfaces, which represents a significant advantage for use in nanocomposites as compared to conventional organoclays which contain up to 40%/wt of organocations. It is expected that this new type of rigid, shear-stiff, clay-based nanoplatelets will be superior for reinforcement when used in composite materials like polymer layered silicate nanocomposites or artificial nacre.

UV‐Cured, Flexible, and Transparent Nanocomposite Coating with Remarkable Oxygen Barrier

A polymer-layered silicate nanocomposite coating is prepared by combining a novel synthetic lithium-hectorite and an UV-curable, cationic polyurethane. Oxygen transmission measurements clearly indicate the supremacy of the lithium-hectorite as compared to a standard montmorillonite. In addition, a very high degree of optical transparency of the nanocomposite coating is achieved, rendering this material highly interesting for flexible packaging and encapsulation applications.

Barrier Properties of Synthetic Clay with a Kilo‐Aspect Ratio

Intrinsic anisometry, the appearance in plate-like pseudocrystals (tactoids) with high aspect ratios, and their rich intercalation chemistry (cation-exchange, swelling) are some of the essential features of clays, which render them interesting as functional particles for a variety of applications. [ 1–3 ] Long before Nielsen’s [ 4 ] essay about the tortuous path theory appeared in the late 1960s, composite materials were prepared of inorganic platelets in a continuous macromolecular phase. [ 5 ] Aside from mechanically toughening of polymeric matrices via the incorporation of stiff platelets, [ 6–9 ] diffusion-barrier, [ 10–12 ] and fl ame retardant applications [ 13 ] are the main focus of current research. Since both, experiments and simulations have emphasized the key importance of high aspect ratios ( α ) of fi llers, in particular for gas permeability, [ 14 , 15 ] material scientists continue hunting for higher α exploring a variety of lamellar materials including graphene. [ 16 ]

Homogeneous precipitation by formamide hydrolysis: Synthesis, reversible hydration, and aqueous exfoliation of the layered double hydroxide (LDH) of Ni and Al

Homogenous precipitation by formamide hydrolysis results in the formation of a formate-intercalated layered double hydroxide (LDH) of Ni(II) and Al(III). The formate-LDH is sensitive to the atmospheric humidity and reversibly exchanges its intercalated water with atmospheric moisture. The hydration/dehydration cycle is complete within a narrow range of 0-30% relative humidity with significant hysteresis and involves a randomly interstratified intermediate phase. When immersed in water, the formate ion grows its hydration sphere (osmotic swelling), eventually leading to the exfoliation of the metal hydroxide layers into lamellar particles having in-plane dimensions of 100-200 nm and a thickness of 9-12 nm. These nanoplatelets restack to thicker tactoids again upon evaporation of the dispersion. The intercalated formate ion can be exchanged with nitrate ions in solution but not with iodide ions. These observations have implications for many applications of LDHs in the area of carbon dioxide sorption and catalysis.

Nanoplatelets of Sodium Hectorite Showing Aspect Ratios of ≈20 000 and Superior Purity

Applying a combination of melt synthesis followed by long-term annealing a fluorohectorite is obtained which is unique with respect to homogeneity, purity, and particle size. Counterintuitively, the hectorite undergoes a disorder-to-order transition upon swelling to the level of the bilayer hydrate. Alkylammonium-exchanged samples show at any chain length only a single basal spacing corroborating a nicely homogeneous layer charge density. Its intracrystalline reactivity improves greatly upon annealing, making it capable to spontaneously and completely disintegrate into single clay lamellae of 1 nm thickness. Realizing exceptional aspect ratios of around 20,000 upon delamination, this synthetic clay will offer unprecedented potential as functional filler in highly transparent nanocomposites with superior gas barrier and mechanical properties.

Direct Synthesis of Inverse Hexagonally Ordered Diblock Copolymer/ Polyoxometalate Nanocomposite Films

Nanostructured inverse hexagonal polyoxometalate composite films were cast directly from solution using poly(butadiene-block-2-(dimethylamino)ethyl methacrylate) (PB-b-PDMAEMA) diblock copolymers as structure directing agents for phosphomolybdic acid (H(3)[PMo(12)O(40)], H(3)PMo). H(3)PMo units are selectively incorporated into the PDMAEMA domains due to electrostatic interactions between protonated PDMAEMA and PMo(3-) anions. Long solvophilic PB chains stabilized the PDMAEMA/H(3)PMo aggregates in solution and reliably prevented macrophase separation. The choice of solvent is crucial. It appears that all three components, both blocks of the diblock copolymer as well as H(3)PMo, have to be soluble in the same solvent which turned out to be tetrahydrofuran, THF. Evaporation induced self-assembly resulted in highly ordered inverse hexagonal nanocomposite films as observed from transmission electron microscopy and small-angle X-ray scattering. This one-pot synthesis may represent a generally applicable strategy for integrating polyoxometalates into functional architectures and devices.

Composites of metal nanoparticles and TiO2 immobilized in spherical polyelectrolyte brushes.

The synthesis and the catalytic activity of nanocomposites consisting of metal nanoparticles (Au, Pt, Pd) and nanoparticles of TiO(2) (anatase) is presented. These composite particles have been synthesized by reduction of the respective metal ions adsorbed on the surface of as-prepared TiO(2) nanoparticles that are immobilized on spherical polyelectrolyte brush particles (SPB) as carrier system. The SPB particles consist of a polystyrene core from which long chains of poly(styrene sodium sulfonate) are grafted. We demonstrate that the metal nanoparticles (such as Au, Pt, and Pd) are only generated on the surface of the anatase particles having a size of ca. 10 nm. These metal NP/TiO(2)@SPB composite particles exhibit a high colloidal stability. They are excellent heterogeneous photocatalysts for the degradation of the dye Rhodamine B under UV irradiation. The photocatalytic activity of the composite particles is 2-5 times higher than that of the pure TiO(2) particles. This finding is traced back to an enhanced adsorption of the dye on the metal@TiO(2) composites.