The formation of PtRu surface alloys by deposition of submonolayer Pt films on a Ru(0001) substrate and subsequent annealing to about 1350 K and the distribution of the Pt atoms in the surface layer were investigated by scanning tunneling microscopy. Quantitative statistical analysis reveals (i) negligible losses of Pt into subsurface regions up to coverages close below 1 monolayer, (ii) a homogeneous distribution of the Pt atoms over the surface, and (iii) the absence of a distinct long-range or short-range order in the surface layer. In addition, the density of specific adsorption ensembles is analyzed as a function of Pt surface content. Possible conclusions on the process for surface alloy formation are discussed. The results are compared with the properties of PtRu bulk alloys and the findings in previous adsorption studies on similar surface alloys (H. Rauscher, T. Hager, T. Diemant, H. Hoster, F. Bautier de Mongeot and R. J. Behm, Surf. Sci., 2007, 601, 4608; T. Diemant, H Rauscher and R. J. Behm, J. Phys. Chem. C, in press).

Tunable and selective hydrogenation of the platform chemical 5-hydroxymethylfurfural into valuable C6 building blocks and liquid fuel additives is achieved with copper-doped porous metal oxides in ethanol. A new catalyst composition with improved hydrogenation/hydrogenolysis activity is obtained by introducing small amounts of ruthenium dopant into the previously reported Cu(0.59) Mg2.34 Al1.00 structure. At a mild reaction temperature (100 °C), 2,5-furandimethanol is obtained with excellent selectivity up to >99%. Higher reaction temperatures (220 °C) favor selective deoxygenation to 2,5-dimethylfuran and minor product 2,5-dimethyltetrahydrofuran with a combined yield as high as 81%. Notably, these high product yields are maintained at a substrate concentration up to 10 wt% and a low catalyst loading. The influence of different alcohol solvents on product selectivity is explored. Furthermore, reaction intermediates formed at different reaction temperatures are identified. The composition of these product mixtures provides mechanistic insight into the nature of the reduction pathways that influence product selectivity. The catalysts are characterized by elemental analysis, TEM, and BET techniques before and after the reaction. Catalyst recycling experiments are conducted in batch and in a continuous-flow setup.

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The controlled growth of metal-organic frameworks (MOFs) over surfaces has been investigated using a variety of surface analytical techniques. The use of microcontact printing to prepare surfaces, patterned with regions capable of nucleating the growth of MOFs, has been explored by employing copper-catalyzed alkyne-azide cycloaddition (CuAAC) to pattern silicon wafers with carboxylic acids, a functional group that has been shown to nucleate the growth of MOFs on surfaces. Upon subjecting the patterned silicon surfaces to solvothermal conditions, MOF thin films were obtained and characterized subsequently by AFM, SEM, and grazing-incidence XRD (GIXRD). Large crystals (∼0.5 mm) have also been nucleated, as indicated by the presence of a bas-relief of the original pattern on one surface of the crystal, suggesting that it is possible to transfer the template surface pattern onto a single crystal of a MOF.

The facile assembly of higher-order nanoarchitectures from simple building blocks is demonstrated by the loading of vesicles into soft amphiphilic nanotubes using osmosis. The nanotubes are constructed from rigid interdigitated bilayers which are capped with vesicles comprising phospholipid-based flexible bilayers. When a hyperosmotic gradient is applied to these vesicle-capped nanotubes, the closed system loses water and the more flexible vesicle bilayer is pulled inwards. This leads to inclusion of vesicles inside the nanotubes without affecting the tube structure, showing controlled reorganization of the self-assembled multicomponent system upon a simple osmotic stimulus.