Norbert Köpfle

An (ultra) high-vacuum compatible sputter source for oxide thin film growth

A miniaturised CF-38 mountable sputter source for oxide and metal thin film preparation with enhanced high-vacuum and ultra-high-vacuum compatibility is described. The all home-built sputtering deposition device allows a high flexibility also in oxidic sputter materials, suitable deposition rates for preparation of films in the nm- and the sub-monolayer regime and excellent reliability and enhanced cleanliness for usage in UHV chambers. For a number of technologically important--yet hardly volatile--materials, the described source represents a significant improvement over thermal deposition techniques like electron-beam- or thermal evaporation, as especially the latter are no adequate tool to prepare atomically clean layers of refractory oxide materials. Furthermore, it is superior to commercially available magnetron sputter devices, especially for applications, where highly reproducible sub-monolayer thin film preparation under very clean UHV conditions is required (e.g., for studying phase boundary effects in catalysis). The device in turn offers the usage of a wide selection of evaporation materials and special target preparation procedures also allow the usage of pressed oxide powder targets. To prove the performance of the sputter-source, test preparations with technologically relevant oxide components, comprising ZrO2 and yttrium-stabilized ZrO2, have been carried out. A wide range of characterization methods (electron microscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, atomic force microscopy, and catalytic testing) were applied to demonstrate the properties of the sputter-deposited thin film systems.

Chemical vapor deposition-prepared sub-nanometer Zr clusters on Pd surfaces: promotion of methane dry reforming

An inverse Pd-Zr model catalyst was prepared by chemical vapor deposition (CVD) using zirconium-t-butoxide (ZTB) as an organometallic precursor. Pd-Zr interaction was then investigated with focus on the correlation of reforming performance with the oxidation state of Zr. As test reactions, dry reforming of methane (DRM) and methanol steam reforming (MSR) were chosen. Depending on treatments, either ZrOxHy or ZrO2 overlayers or Zr as sub-nanometer clusters could be obtained. Following the adsorption of ZTB on Pd(111), a partially hydroxylated Zr4+-containing layer was formed, which can be reduced to metallic Zr by thermal annealing in ultrahigh vacuum, leading to redox-active Zr0 sub-nanometer clusters. Complementary density functional theoretical (DFT) calculations showed that a single layer of ZrO2 on Pd(111) can be more easily reduced toward the metallic state than a double- and triple layer. Also, the initial and resulting layer compositions greatly depend on gas environment. The lower the water background partial pressure, the faster and more complete the reduction of Zr4+ species to Zr0 on Pd takes place. Under methanol steam reforming conditions, water activation by hydroxylation of Zr occurs. In excess of methanol, strong coking is induced by the Pd/ZrOxHy interface. In contrast, dry reforming of methane is effectively promoted if these initially metallic Zr species are present in the pre-catalyst, leading to a Pd/ZrOxHy phase boundary by oxidative activation under reaction conditions. These reaction-induced active sites for DRM are stable with respect to carbon blocking or coking. In essence, Zr doping of Pd opens specific CO2 activation channels, which are absent on pure metallic Pd.

Boosting Hydrogen Production from Methanol and Water by in situ Activation of Bimetallic Cu−Zr Species

A bimetallic Cu/Cu51Zr14 precatalyst, activated in situ, for hydrogen generation from methanol and water provides very high CO2 selectivity (>99.9 %) and high H2 yields. Referenced to the geometric surface area of our model surface, higher activity of at least one order of magnitude was observed in comparison to supported Cu/ZrO2 and Cu/ZnO/ZrO2 catalysts. Evolution of structural activation monitored by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), and electron microscopy indicates transformation of the bimetallic Cu/Cu51Zr14 precatalyst into an active, selective, and self‐stabilizing state with coexistence of dispersed Cu and partially hydroxylated tetragonal ZrO2. The outstanding performance is assigned to the presence of a high interface‐site concentration following in situ decomposition of the intermetallic compound. These active sites result from the cooperation of Cu, responsible for methanol activation, and tetragonal ZrO2, which activates the water by surface hydroxylation.

Zirconium‐Assisted Activation of Palladium To Boost Syngas Production by Methane Dry Reforming

Abstract C‐saturated Pd0 nanoparticles with an extended phase boundary to ZrO2 evolve from a Pd0Zr0 precatalyst under CH4 dry reforming conditions. This highly active catalyst state fosters bifunctional action: CO2 is efficiently activated at oxidic phase boundary sites and PdxC provides fast supply of C‐atoms toward the latter.