The fundamental question as to the relative importance of interparticle superexchange versus dipolar interaction between oxide magnetic particles in direct physical contact is addressed by examining the magnetic properties of a series of compacted samples comprising identical maghemite particles (8 nm in diameter) coated by nonmagnetic shells (oleic acid or silica) of varying thickness that control the distance between the magnetic cores and hence the packing density (particle volume fraction). A remarkably narrow maghemite particle size distribution is established by electron microscopy and small-angle X-ray scattering. The series includes a sample made up of bare particles in a random-close-packed configuration (therefore in direct contact) that exhibits ideal superspin-glass behavior with a relatively high freezing transition temperature. It is shown that interparticle superexchange interactions between the nanoparticles in this sample play a minor role compared to classical dipolar interactions in establishing the collective, superspin-glass state. This follows from the freezing temperature of the most concentrated samples in the series (those with 0 ≤ shell thickness < 3 nm), which are found to vary in direct proportionality with the volume fraction of the maghemite cores and therefore with the strength of dipolar interactions.

A simple single-phase material, a random close-packed (volume fraction 67%) ensemble of highly monodisperse bare maghemite (γ-Fe2O3) nanoparticles, is shown to exhibit ideal superspin-glass behavior (mimicking that of model spin-glasses), namely, an unprecedentedly sharp onset of the absorption component of the ac susceptibility, narrow memory dips in the zero-field-cooled magnetization and a spin-glass characteristic field-dependence of the magnetic susceptibility. This ideal behavior is attributed to the remarkably narrow dispersion in particle size and to the highly dense and spatially homogeneous configuration ensured by the random close-packed arrangement. This material is argued to constitute the closest nanoparticle analogue to a conventional (atomic) magnetic state found to date.

Copper and zirconium oxide clusters were highly dispersed on mesocellular siliceous foam (MCF), a mesoporous silica support with ultra large, interconnected nanopores. These catalysts (denoted as Cu/MCF and Zr/MCF) were separately loaded into two fixed bed reactors as catalysts for the conversion of ethanol (EtOH) to 1,3-butadiene (BD). Under optimal conditions, high BD selectivity (up to 73%) and ethanol conversion (up to 96%) were achieved at weight hourly space velocities of 1.5 and 3.7 h −1 . This translates to an unprecedented productivity of 1.4 g BD /g catalyst h −1 (208 g BD /l catalyst h −1 ). The high catalytic performance is attributed to the highly selective and active catalysts. The EtOH dehydrogenation activity of Cu/MCF could be accurately controlled in the first reactor, which delivers a fixed ratio of the acetaldehyde/EtOH mixture to Zr/MCF in the second reactor. The optimal ratio minimizes EtOH dehydration to ethylene by Zr/MCF, while maximizing the selectivity to BD. MCF was found to be superior over commercial porous silica in terms of EtOH conversion, BD selectivity, and tolerance to coking. High BD selectivity was maintained with a slight decrease in EtOH conversion over 42 h, which was readily restored upon regeneration by thermal treatment in air.

For efficient direct amide condensations, a new class of catalysts are developed by immobilizing boronic acids on mesocellular siliceous foam. Associated with their large pores, the microenvironments surrounding the immobilized active species greatly influence the catalytic activity. The fluoroalkyl moieties on the silica surface significantly enhance the catalytic performance along with easy recovery and reuse. This approach proposes a potential way to optimize various types of silica-supported catalysts.

Ruthenium-based metathesis catalysts immobilized on mesocellular siliceous foam (MCF) bearing large nanopores proved highly efficient and selective for macrocyclic ring-closing metathesis (RCM). Kinetic studies revealed that the homogeneous counterpart exhibited far higher activity that accounted for more oligomerization pathways and resulted in less macrocyclization products. Meanwhile, the immobilized catalysts showed lower conversion rates leading to higher yields of macrocyclic products in a given reaction time, with conversion rates and yields dependent upon pore size, catalyst loading density, and linker length. The macrocycle formations via RCM were accelerated by increasing the pore size and decreasing the catalyst loading density while retaining the comparably high yield. The catalysts immobilized on MCF, of which silica surface is rigid and pores are relatively large, showed high conversion rates and yields compared with an analogue immobilized on TentaGel resins, of which backbone becomes flexible upon swelling in the reaction medium. It is noteworthy that the selectivity for the macrocyclic RCM can be significantly improved by tuning the catalyst initiation rates via immobilization onto the support materials in which well-defined three-dimentional network of large nanopores are deployed.

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Nanoboxes with a porous MnO core and amorphous TiO2 shell have been synthesized via a wet-chemistry method for the first time.

γ-Fe(2)O(3) nanoparticles were formed inside the cage-like pores of mesocellular foam (MCF). These magnetic nanoparticles showed a uniform size distribution that could be easily controlled by the MCF pore size, as well as by the hydrocarbon chain length used for MCF surface modification. Throughout the entrapment process, the pore structure and surface area of the MCF remained intact. The resulting magnetic MCF facilitated the immobilization of biocatalysts, homogeneous catalysts, and nanoclusters. Moreover, the MCF allowed for facile catalyst recovery by using a simple magnet. The supported catalysts exhibited excellent catalytic efficiencies that were comparable to their homogeneous counterparts.