Mesostructured ZnO/Au nanoparticle composites with enhanced photocatalytic activity

Ease of catalyst separation from reaction mixtures represents a significant advantage in heterogeneous photocatalytic wastewater treatment. However, the activity of the catalyst strongly depends on its surface-to-volume ratio. Here, we present an approach based on cylindrical polybutadiene-block-poly(2-vinylpyridine) polymer brushes as template, which can be simultaneously loaded with zinc oxide (ZnO) and gold (Au) nanoparticles. Pyrolytic template removal of the polymer yields in mesostructured ZnO/Au composites, showing higher efficiencies in the photocatalytic degradation of ciprofloxacin and levofloxacin (generic antibiotics present in clinical wastewater) as compared to neat mesostructured ZnO. Upscaling of the presented catalyst is straightforward promising high technical relevance

Enhancing the Catalytic Activity of Palladium Nanoparticles via Sandwich-Like Confinement by Thin Titanate Nanosheets

As atomically thin oxide layers deposited on flat (noble) metal surfaces have been proven to have a significant influence on the electronic structure and thus the catalytic activity of the metal, we sought to mimic this architecture at the bulk scale. This could be achieved by intercalating small positively charged Pd nanoparticles of size 3.8 nm into a nematic liquid crystalline phase of lepidocrocite-type layered titanate. Upon intercalation the galleries collapsed and Pd nanoparticles were captured in a sandwichlike mesoporous architecture showing good accessibility to Pd nanoparticles. On the basis of X-ray photoelectron spectroscopy (XPS) and CO diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) Pd was found to be in a partially oxidized state, while a reduced Ti species indicated an electronic interaction between nanoparticles and nanosheets. The close contact of titanate sandwiching Pd nanoparticles, moreover, allows for the donation of a lattice oxygen to the noble metal (inverse spillover). Due to the metal–support interactions of this peculiar support, the catalyst exhibited the oxidation of CO with a turnover frequency as high as 0.17 s–1 at a temperature of 100 °C

In Depth Insights into the Key Steps of Delamination of Charged 2D Nano Materials

Delamination is a key step to obtain individual layers from inorganic layered materials needed for fundamental studies and applications. For layered van-der-Waals materials like graphene the adhesion forces are small allowing for mechanical exfoliation, whereas for ionic layered materials like layered silicates the energy to separate adjacent layers is considerably higher. Quite counter intuitively, we show for a synthetic layered silicate (Na0.5-hectorite) that a scalable and quantitative delamination by simple hydration is possible for high and homogeneous charge density, even for aspect ratios as large as 20000. A general requirement is the separation of adjacent layers by solvation to a distance where layer interactions become repulsive (Gouy-Chapman length). Further hydration up to 34 nm leads to the formation of a highly ordered lamellar liquid crystalline phase (Wigner crystal). Up to 8 higher-order reflections indicate excellent positional order of individual layers. The Wigner crystal melts when the interlayer separation reaches the Debye length, where electrostatic interactions between adjacent layers are screened. The layers become weakly chargecorrelated. This is indicated by fulfilling the classical Hansen-Verlet and Lindeman criteria for melting. We provide insight into the requirements for layer separation and controlling the layer distances for a broad range of materials and outline an important pathway for the integration of layers into devices for advanced applications

Nematic suspension of a microporous layered silicate obtained by forceless spontaneous delamination via repulsive osmotic swelling for casting high-barrier all-inorganic films

Exploiting the full potential of layered materials for a broad range of applications requires delamination into functional nanosheets. Delamination via repulsive osmotic swelling is driven by thermodynamics and represents the most gentle route to obtain nematic liquid crystals consisting exclusively of single-layer nanosheets. This mechanism was, however, long limited to very few compounds, including 2:1-type clay minerals, layered titanates, or niobates. Despite the great potential of zeolites and their microporous layered counterparts, nanosheet production is challenging and troublesome, and published procedures implied the use of some shearing forces. Here, we present a scalable, eco-friendly, and utter delamination of the microporous layered silicate ilerite into single-layer nanosheets that extends repulsive delamination to the class of layered zeolites. As the sheet diameter is preserved, nematic suspensions with cofacial nanosheets of ≈9000 aspect ratio are obtained that can be cast into oriented films, e.g., for barrier applications

Nanoparticles Supported on Sub-Nanometer Oxide Films : Scaling Model Systems to Bulk Materials

Ultrathin layers of oxides deposited on atomically flat metal surfaces have been shown to significantly influence the electronic structure of the underlying metal, which in turn alters the catalytic performance. Upscaling of the specifically designed architectures as required for technical utilization of the effect has yet not been achieved. Here, we apply liquid crystalline phases of fluorohectorite nanosheets to fabricate such architectures in bulk. Synthetic sodium fluorohectorite, a layered silicate, when immersed into water spontaneously and repulsively swells to produce nematic suspensions of individual negatively charged nanosheets separated to more than 60 nm, while retaining parallel orientation. Into these galleries oppositely charged palladium nanoparticles were intercalated whereupon the galleries collapse. Individual and separated Pd nanoparticles were thus captured and sandwiched between nanosheets. As suggested by the model systems, the resulting catalyst performed better in the oxidation of carbon monoxide than the same Pd nanoparticles supported on external surfaces of hectorite or on a conventional Al2O3 support. XPS confirmed a shift of Pd 3d electrons to higher energies upon coverage of Pd nanoparticles with nanosheets to which we attribute the improved catalytic performance. DFT calculations showed increasing positive charge on Pd weakened CO adsorption and this way damped CO poisoning

Segregation by thermal diffusion of an intruder in a moderately dense granular fluid

A solution of the inelastic Enskog equation that goes beyond the weak dissipation limit and applies for moderate densities is used to determine the thermal diffusion factor of an intruder immersed in a dense granular gas under gravity. This factor provides a segregation criterion that shows the transition between the Brazil-nut effect (BNE) and the reverse Brazil-nut effect (RBNE) by varying the parameters of the system (masses, sizes, density and coefficients of restitution). The form of the phase-diagrams for the BNE/RBNE transition depends sensitively on the value of gravity relative to the thermal gradient, so that it is possible to switch between both states for given values of the parameters of the system. Two specific limits are considered with detail: (i) absence of gravity, and (ii) homogeneous temperature. In the latter case, after some approximations, our results are consistent with previous theoretical results derived from the Enskog equation. Our results also indicate that the influence of dissipation on thermal diffusion is more important in the absence of gravity than in the opposite limit. The present analysis extends previous theoretical results derived in the dilute limit case [V. Garz\'o, Europhys. Lett. {\bf 75}, 521 (2006)] and is consistent with the findings of some recent experimental results.Comment: 10 figure