X-ray standing wave characterization of the strong metal-support interaction in Co/TiOx model catalysts.

The strong metal-support interaction (SMSI) is a phenomenon observed in supported metal catalyst systems in which reducible metal oxide supports can form overlayers over the surface of active metal nanoparticles (NPs) under a hydrogen (H2) environment at elevated temperatures. SMSI has been shown to affect catalyst performance in many reactions by changing the type and number of active sites on the catalyst surface. Laboratory methods for the analysis of SMSI at the nanoparticle-ensemble level are lacking and mostly based on indirect evidence, such as gas chemisorption. Here, we demonstrate the possibility to detect and characterize SMSIs in Co/TiOx model catalysts using the laboratory X-ray standing wave (XSW) technique for a large ensemble of NPs at the bulk scale. We designed a thermally stable MoNx/SiNx periodic multilayer to retain XSW generation after reduction with H2 gas at 600°C. The model catalyst system was synthesized here by deposition of a thin TiOx layer on top of the periodic multilayer, followed by Co NP deposition via spare ablation. A partial encapsulation of Co NPs by TiOx was identified by analyzing the change in Ti atomic distribution. This novel methodological approach can be extended to observe surface restructuring of model catalysts in situ at high temperature (up to 1000°C) and pressure (≤3 mbar), and can also be relevant for fundamental studies in the thermal stability of membranes, as well as metallurgy.

Deep reactive ion etching of cylindrical nanopores in silicon for photonic crystals.

Periodic arrays of deep nanopores etched in silicon by deep reactive ion etching are desirable structures for photonic crystals and other nanostructures for silicon nanophotonics. Previous studies focused on realizing as deep as possible nanopores with as high as possible aspect ratios. The resulting nanopores suffered from structural imperfections of the nanopores, such as mask undercut, uneven and large scallops, depth dependent pore radii and tapering. Therefore, our present focus is to realize nanopores that have as cylindrical as possible shapes, in order to obtain a better comparison of nanophotonic observations with theory and simulations. To this end in our 2-step Bosch process we have improved the mask undercut, the uneven scallops, pore widening and positive tapering by optimizing a plethora of parameters such as the etch step time, capacitively coupled plasma (ion energy) and pressure. To add further degrees of control, we implemented a 3-step DREM (deposit, remove, etch, multistep) process. Optimization of the etching process results in cylindrical nanopores with a diameter in the range between 280 and 500 nm and a depth around 7µm, corresponding to high depth-to-diameter aspect ratios between 14 and 25, that are very well suited for the realization of silicon nanophotonic structures.

Highly Sensitive Protein Detection by Asymmetric Mach-Zehnder Interferometry for Biosensing Applications.

The sensitivity and performance of an asymmetric Mach-Zehnder interferometer (aMZI) were compared to those of quartz crystal microbalance with dissipation (QCM-D). The binding of streptavidin to sensor chips coated with poly-l-lysine (PLL), modified with biotin and oligoethyleneglycol (OEG) (PLL-biotin), was used to compare the binding signals obtained from both technologies. PLL-biotin proved to be an efficient method to add bioreceptors to both the QCM-D and aMZI chips. The final, saturated value of streptavidin binding was compared with those from aMZI (253 ng cm-2) and QCM-D (460 ng cm-2). These values were then used to evaluate that 45% of the measured streptavidin mass in the QCM-D came from hydrodynamically coupled water. Importantly, the signal-to-noise ratio of the aMZI was found to be 200 times higher than that of the QCM-D. These results indicate the potential of the aMZI platform for highly sensitive and accurate biosensing applications.

Structures of a Clathrate Hydrate Former, Inhibitor, and Synergist in Water.

SANS studies are reported for aqueous THF at the 1:17 clathrate hydrate-forming composition and on aqueous solutions of the synergist 2-butoxyethanol. Addition of the clathrate hydrate inhibitor polyvinylcaprolactam and a dimeric model compound, 1,3-bis(caprolactamyl)butane, show that the inhibitors do not significantly affect the solution structures of these two important species in clathrate hydrate formation and inhibition. The SANS studies show that 1,3-bis(caprolactamyl)butane is a good model for polyvinylcaprolactam, and both the polymer and model compound exhibit hydrogen bonding interactions with water but do not interact significantly with 2-butoxyethanol in aqueous solution.