Interaction of water and carbon monoxide with MnO(001) thin films on Au(111).

Atomically defined MnO(001) thin films were grown on an Au(111) substrate, and their interaction with water (D2O) was investigated by infrared reflection absorption spectroscopy (IRAS) and thermal desorption spectroscopy (TDS). Carbon monoxide adsorption experiments were performed to probe surface atoms and defects on oxide films. Next, water interaction was investigated from which an associative binding pathway and a dissociative binding pathway were revealed, where the water molecules adsorb at terraces and water dissociation takes place at oxygen vacancies mediated by nearby Mn2+ sites. The IRAS data are supported by TDS experiments, which also manifest the importance of defects in the adsorption characteristics of MnO.

Surface photovoltage dynamics at passivated silicon surfaces: influence of substrate doping and surface termination.

We have monitored the temporal evolution of the band bending at controlled silicon surfaces after a fs laser pump excitation. Time-resolved surface photo-voltage (SPV) experiments were performed using time resolved photoemission spectroscopy with time resolution of about 30 ns. To disentangle the influence of doping and surface termination on SPV dynamics, we compare the results obtained on two surface terminations: the water saturated (H,OH)-Si(001) surface and the thermally oxidized Si(001) one. The SPV dynamics were explored as a function of laser fluence and as a function of time for the two surface terminations at given doping levels. The return to equilibrium involves a characteristic time in the 0.1 µs to 10 µs range, depending on the surface termination and bulk doping. Exploring several laser fluences, different SPV regimes were found for the two surface terminations at given doping levels. For low laser fluence the SPV dynamic follows the commonly accepted thermionic model. At higher fluence, the SPV signal reaches a saturation value, and if the fluence is further increased, the decay time of the SPV increases and can no longer be explained by a thermionic model alone.

HIPPIE: a new platform for ambient-pressure X-ray photoelectron spectroscopy at the MAX IV Laboratory.

HIPPIE is a soft X-ray beamline on the 3 GeV electron storage ring of the MAX IV Laboratory, equipped with a novel ambient-pressure X-ray photoelectron spectroscopy (APXPS) instrument. The endstation is dedicated to performing in situ and operando X-ray photoelectron spectroscopy experiments in the presence of a controlled gaseous atmosphere at pressures up to 30 mbar [1 mbar = 100 Pa] as well as under ultra-high-vacuum conditions. The photon energy range is 250 to 2200 eV in planar polarization and with photon fluxes >1012 photons s-1 (500 mA ring current) at a resolving power of greater than 10000 and up to a maximum of 32000. The endstation currently provides two sample environments: a catalysis cell and an electrochemical/liquid cell. The former allows APXPS measurements of solid samples in the presence of a gaseous atmosphere (with a mixture of up to eight gases and a vapour of a liquid) and simultaneous analysis of the inlet/outlet gas composition by online mass spectrometry. The latter is a more versatile setup primarily designed for APXPS at the solid-liquid (dip-and-pull setup) or liquid-gas (liquid microjet) interfaces under full electrochemical control, and it can also be used as an open port for ad hoc-designed non-standard APXPS experiments with different sample environments. The catalysis cell can be further equipped with an IR reflection-absorption spectrometer, allowing for simultaneous APXPS and IR spectroscopy of the samples. The endstation is set up to easily accommodate further sample environments.

High-Density Isolated Fe1O3 Sites on a Single-Crystal Cu2O(100) Surface.

Single-atom catalysts have recently been subject to considerable attention within applied catalysis. However, complications in the preparation of well-defined single-atom model systems have hampered efforts to determine the reaction mechanisms underpinning the reported activity. By means of an atomic layer deposition method utilizing the steric hindrance of the ligands, isolated Fe1O3 motifs were grown on a single-crystal Cu2O(100) surface at densities up to 0.21 sites per surface unit cell. Ambient pressure X-ray photoelectron spectroscopy shows a strong metal-support interaction with Fe in a chemical state close to 3+. Results from scanning tunneling microscopy and density functional calculations demonstrate that isolated Fe1O3 is exclusively formed and occupies a single site per surface unit cell, coordinating to two oxygen atoms from the Cu2O lattice and another through abstraction from O2. The isolated Fe1O3 motif is active for CO oxidation at 473 K. The growth method holds promise for extension to other catalytic systems.

Particle size effect on the Langmuir-Hinshelwood barrier for CO oxidation on regular arrays of Pd clusters supported on ultrathin alumina films.

The Langmuir-Hinshelwood barrier (ELH) and the pre-exponential factor (νLH) for CO oxidation have been measured at high temperatures on hexagonal arrays of Pd clusters supported on an ultrathin alumina film on Ni3Al (111). The Pd clusters have a sharp size distribution, and the mean sizes are 174 ± 13, 360 ± 19, and 768 ± 28 atoms. ELH and νLH are determined from the initial reaction rate of a CO molecular beam with a saturation layer of adsorbed oxygen on the Pd clusters measured at different temperatures [493 ≤ T(K) ≤ 613]. The largest particles (3.5 nm) give values of ELH and νLH similar to those measured on Pd (111) [T. Engel and G. Ertl, J. Chem. Phys. 69, 1267 (1978)]. However, smaller particles (2.7 and 2.1 nm) show very different behaviors. The origin of this size effect is discussed in terms of variation of the electronic structure and of the atomic structure of the Pd clusters.

Soft X-ray Heterogeneous Radiolysis of Pyridine in the Presence of Hydrated Strontium-Hydroxyhectorite and its Monitoring by Near-Ambient Pressure Photoelectron Spectroscopy.

The heterogeneous radiolysis of organic molecules in clays is a matter of considerable interest in astrochemistry and environmental sciences. However, little is known about the effects of highly ionizing soft X-rays. By combining monochromatized synchrotron source irradiation with in situ Near Ambient Pressure X-ray Photoelectron Spectroscopy (in the mbar range), and using the synoptic view encompassing both the gas and condensed phases, we found the water and pyridine pressure conditions under which pyridine is decomposed in the presence of synthetic Sr2+-hydroxyhectorite. The formation of a pyridine/water/Sr2+ complex, detected from the Sr 3d and N 1s core-level binding energies, likely presents a favorable situation for the radiolytic breaking of the O-H bond of water molecules adsorbed in the clay and the subsequent decomposition of the molecule. However, decomposition stops when the pyridine pressure exceeds a critical value. This observation can be related to a change in the nature of the active radical species with the pyridine loading. This highlights the fact that the destruction of the molecule is not entirely determined by the properties of the host material, but also by the inserted organic species. The physical and chemical causes of the present observations are discussed.

Preparation and structure of Fe-containing aluminosilicate thin films.

In attempts to fabricate model systems of Fe-containing aluminosilicates, we studied the incorporation of iron into silicate and aluminosilicate bilayer films grown on Ru(0001). Structural characterization was performed by low energy electron diffraction, X-ray photoelectron spectroscopy, infrared reflection-absorption spectroscopy and scanning tunneling microscopy. The experimental results show that even at low concentrations Fe does not randomly substitute Si(Al) cations in the silicate framework, but segregates into a pure silicate (aluminosilicate) phase and an Fe-silicate phase which is formed by an FeO(111)-like layer underneath a silicate layer. At high Fe/(Si + Al) molar ratios, the resulting films showed two phases depending on the annealing temperature. In both phases, the surface exposes a silicate layer and the bottom layer is dominated by FeO. The Al ions seem to be present in the bottom layer at relatively low oxidation temperatures, but segregate as alumina clusters at the surface at higher temperatures. The results suggest that the formation of in-frame Fe species in silicalites and zeolites is thermodynamically unfavourable. This study provides further steps towards the rational design of model systems for studying surface chemistry of a wide class of layered minerals.

Catechol-O-methyltransferase in complex with substituted 3'-deoxyribose bisubstrate inhibitors.

The biological activity of catechol neurotransmitters such as dopamine in the synapse is modulated by transporters and enzymes. Catechol-O-methyltransferase (COMT; EC 2.1.1.6) inactivates neurotransmitters by catalyzing the transfer of a methyl group from S-adenosylmethionine to catechols in the presence of Mg²âº. This pathway also inactivates L-DOPA, the standard therapeutic for Parkinson's disease. Depletion of catechol neurotransmitters in the prefrontal cortex has been linked to schizophrenia. The inhibition of COMT therefore promises improvements in the treatment of these diseases. The concept of bisubstrate inhibitors for COMT has been described previously. Here, ribose-modified bisubstrate inhibitors were studied. Three high-resolution crystal structures of COMT in complex with novel ribose-modified bisubstrate inhibitors confirmed the predicted binding mode but displayed subtle alterations at the ribose-binding site. The high affinity of the inhibitors can be convincingly rationalized from the structures, which document the possibility of removing and/or replacing the ribose 3'-hydroxyl group and provide a framework for further inhibitor design.