In its nanoparticulate form, corundum (α-Al2O3) could lead to several applications. However, its production into nanoparticles (NPs) is greatly hampered by the high activation energy barrier for its formation from cubic close-packed oxides and the sporadic nature of its nucleation. We report a simple synthesis of nanometer-sized α-Al2O3 (particle diameter ~13 nm, surface areas ~140 m2 g−1) by the mechanochemical dehydration of boehmite (γ-AlOOH) at room temperature. This transformation is accompanied by severe microstructural rearrangements and might involve the formation of rare mineral phases, diaspore and tohdite, as intermediates. Thermodynamic calculations indicate that this transformation is driven by the shift in stability from boehmite to α-Al2O3 caused by milling impacts on the surface energy. Structural water in boehmite plays a crucial role in generating and stabilizing α-Al2O3 NPs.
Supported catalysts are among the most important classes of catalysts.T hey are typically prepared by wetchemical methods,s uch as impregnation or co-precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of asupport oxide leads in many cases to supported catalysts with particles in the nanometer size range.V arious supports,i ncluding TiO 2 ,A l 2 O 3 ,F e 2 O 3 ,a nd Co 3 O 4 ,a nd different metals,s uch as Au,P t, Ag,C u, and Ni, were studied, and for eacho ft he supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts.T he method thus provides as imple and cost-effective alternative to the conventionally used impregnation methods.
Mechanochemical activation of solids can lead to a strong increase in their activity as catalysts in heterogeneously catalyzed reactions. In the following, we report on the effects of solid catalyst activation during ball milling that lead to oscillatory behavior in CO and CO 2 formation during propene oxidation. The oscillations arise under in situ ball milling conditions over chromium(III) oxide (Cr 2 O 3 ) and cerium(IV) oxide (CeO 2 ), respectively. The experiments were conducted under continuous gas flow at ambient pressure and temperature, using both a modified steel and a tungsten carbide milling vessel. Abrasion of particles from the steel milling vessel could be eliminated as the sole cause for the oscillations through substitution by a tungsten carbide milling vessel. The intensity and frequency of oscillations are shown to be dependent on the propene-to-oxygen ratio, the milling frequency, milling ball size and metal oxide used. Overall, Cr 2 O 3 shows higher activity for oscillatory propene combustion under in situ mechanical activation than CeO 2 .
Single chains of metal atoms are expected to be perfect onedimensional nanowires in nanotechnology, due to their quantum nature including tunable electronic or spin coupling strengths. However, it is still rather difficult to fabricate such nanowires with metallic atoms under directional and separation control. Here, we succeeded in building higherorder single diamondoid-chains from the lower-order chains using a chemically well-controlled approach that employs diamondoids on metal surfaces. This approach results in higher-order diamondoid double chains by linking two neighboring single chains, and ultimately forms a central chain consisting of single Cu atoms suspended by the diamantane framework. The suspended Cu atoms are placed above the metal surface with a periodic distance of 0.67 ± 0.01 nm. Our bottom-up approach will allow detailed experimental investigations of the properties of these exciting suspended metal atoms (for example, quantized conductance, spin coupling, as well as transfer, etc.). Furthermore, we also identified different spatial configurations on the metal surfaces in on-surface reaction processes using high-resolution AFM imaging and density functional theory computations. Our findings broaden the on-surface synthesis concept from 2D planar aromatic molecules to 3D bulky aliphatic molecules.
Supported catalysts are among the most important classes of catalysts. They are typically prepared by wet‐chemical methods, such as impregnation or co‐precipitation. Here we disclose that dry ball milling of macroscopic metal powder in the presence of a support oxide leads in many cases to supported catalysts with particles in the nanometer size range. Various supports, including TiO2, Al2O3, Fe2O3, and Co3O4, and different metals, such as Au, Pt, Ag, Cu, and Ni, were studied, and for each of the supports and the metals, highly dispersed nanoparticles on supports could be prepared. The supported catalysts were tested in CO oxidation, where they showed activities in the same range as conventionally prepared catalysts. The method thus provides a simple and cost‐effective alternative to the conventionally used impregnation methods.
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