The role of metal-support interaction for CO-free hydrogen from low temperature ethanol steam reforming on Rh-Fe catalysts.

Rh-Fe catalysts supported on Ca-Al2O3, MgO and ZrO2 were evaluated in ethanol steam reforming at 623 K and compared to Rh catalysts on the same supports without iron promotion. The metal-support interaction among the three entities, i.e. Rh ↔ Fe2O3 ← support (ZrO2, MgO and Ca-Al2O3) was investigated using H2-chemisorption, TEM, XPS and in situ techniques such as DRIFTS, temperature-resolved XRD and XAS. As compared to the unpromoted Rh catalysts on the same supports, the CO selectivity is depressed in the presence of iron on Rh/MgO and Rh/Ca-Al2O3, the latter being significantly superior. The role of metal-support interaction for CO-free hydrogen generation was unravelled using a combination of techniques. It was found that the reducibility of iron oxide determines the extent of the strong metal support interaction between Rh and Fe2O3 and the reducibility of iron oxide was affected by the support. On Rh-Fe/Ca-Al2O3, a good balance of the interaction between Rh, Fe2O3 and Ca-Al2O3 prevents strong metal support interaction between Rh and Fe2O3 and thus promotes CO elimination via water-gas-shift reaction on Rh-FexOy sites.

Interaction of magnetic transition metal dimers with spin-polarized hydrogenated graphene.

The coadsorption of hydrogen and transition metal dimers Fe2, Co2, Ni2, and FeCo on graphene is investigated using density functional theory calculations. Our work is motivated by observations that the magnetic moments of these transition metal dimers are large and that hydrogen adsorption partitions the graphene lattice into magnetic subdomains. Thus, we expect the magnetic dimers to interact strongly with the lattice. Our results show that the majority-spin direction of the lattice electronic states depends upon the dimer identity, the lattice spin polarization being in the same direction as the dimer spin polarization for Fe2 and FeCo, but opposite for Co2 and Ni2. We can understand this by examining the electronic density of states of the dimer and the lattice. We also show that coadsorption significantly increases the adsorption energies of both dimer and hydrogen leading to a more strongly-adsorbed dimer, while the bond length and magnetic moment of the upper dimer atom, the latter important for potential magnetic storage applications, are negligibly changed. Our work shows that the coadsorbed hydrogen and metal dimer interact over a long-range, this interaction being mediated by the hydrogen-induced spin-polarization of the graphene lattice. We obtain general insight into how the elemental identity of these magnetic dimers determines the spin-polarized states on the hydrogenated graphene lattice. These results could be important for potential applications of magnetic properties of decorated graphene lattices.

Ion-orbital coupling in Car-Parrinello calculations of hydrogen-bond vibrational dynamics: case study with the NH3-HCl dimer.

We have performed Car-Parrinello molecular dynamics (CPMD) calculations of the hydrogen-bonded NH(3)-HCl dimer. Our main aim is to establish how ionic-orbital coupling in CPMD affects the vibrational dynamics in hydrogen-bonded systems by characterizing the dependence of the calculated vibrational frequencies upon the orbital mass in the adiabatic limit of Car-Parrinello calculations. We use the example of the NH(3)-HCl dimer because of interest in its vibrational spectrum, in particular the magnitude of the frequency shift of the H-Cl stretch due to the anharmonic interactions when the hydrogen bond is formed. We find that an orbital mass of about 100 a.u. or smaller is required in order for the ion-orbital coupling to be linear in orbital mass, and the results for which can be accurately extrapolated to the adiabatic limit of zero orbital mass. We argue that this is general for hydrogen-bonded systems, suggesting that typical orbital mass values used in CPMD are too high to accurately describe vibrational dynamics in hydrogen-bonded systems. Our results also show that the usual application of a scaling factor to the CPMD frequencies to correct for the effects of orbital mass is not valid. For the dynamics of the dimer, we find that the H-Cl stretch and the N-H-Cl bend are significantly coupled, suggesting that it is important to include the latter degree of freedom in quantum dynamical calculations. Results from our calculations with deuterium-substitution show that both these degrees of freedom have significant anharmonic interactions. Our calculated frequency for the H-Cl stretch using the Becke-exchange Lee-Yang-Parr correlation functional compares reasonably well with a previous second-order Møller-Plesset calculation with anharmonic corrections, although it is low compared to the experimental value for the dimer trapped in a neon-matrix.

Revisiting the vibrational spectra of silicon hydrides on Si(100)-(2x1) surface: What is on the surface when disilane dissociates?

Even though the decomposition of disilane on silicon surfaces has been extensively studied, the molecular mechanism for its decomposition has not been fully resolved. The general view motivated partly by spectroscopic data is that decomposition occurs through silicon-silicon bond dissociation although there is evidence from kinetics that silicon-hydrogen bond dissociation is important, and perhaps even dominant. Thus, we reexamine the assignment of the experimental vibrational peaks observed in disilane and silane adsorption in order to assess the evidence for the silicon hydride species that are formed during decomposition. We calculate the vibrational density of states for a number of silicon hydride species on the Si(100)-(2x1) surface using Car-Parrinello molecular dynamics. We obtain the calculated vibrational frequency in the adiabatic limit by extrapolating to zero orbital mass, calibrating our method using the well-established monohydride peak. The calculated vibrational frequencies of the monohydride are in good agreement experimental data. Our results show that the spectroscopic data for silicon hydrides does not preclude the occurrence of Si(2)H(5) on the surface thus providing evidence for silicon-hydrogen bond dissociation during disilane adsorption. Specifically, we find that an experimentally observed vibrational peak at 2150 cm(-1) that has generally been attributed to the trihydride SiH(3) is more likely to be due to Si(2)H(5). Our results also clear up the assignment of two peaks for monohydride species adsorbed at the edge of a growing terrace, and a peak for the dihydride species adsorbed in the interdimer configuration.

Sputter roughening of inhomogeneous surfaces: impurity pinning and nanostructure shape selection.

A model is proposed for sputter roughening of inhomogeneous systems with slowly sputtered impurity particles randomly distributed in the bulk. Surface inhomogeneity, which develops as a result of coupling between the time evolution of the local surface impurity concentration and the local surface shape, is tuned by changing the dependence of the sputtering probability upon impurity concentration. In 1+1 dimensions, we find long-time scaling exponents that are consistent with Kardar-Parisi-Zhang (KPZ) values. However, for a range of surface inhomogeneity, impurity pinning results in a persistent growth regime where the surface roughens rapidly. We correlate this rapid roughening to fluctuations of the impurity concentration at the surface. Roughening in this regime leads to the formation of cones whose shape is determined by material property and sputtering flux, suggesting a unique method of nanostructure fabrication. In 2+1 dimensions, a similar variation of the roughening behavior with surface inhomogeneity is observed. For small surface inhomogeneity, there is an initial exponential roughening followed by power-law roughening with an effective growth exponent much smaller than KPZ. For larger surface inhomogeneity two power-law roughening regimes are observed, with an initial rapid roughening that crosses over to slower roughening; the effective exponent in each of these regimes increases with surface inhomogeneity. The surface morphology observed in the simulations is considerably noisier than experimental data for InP and GaSb. Our model shows noisy nonlinear pattern formation in contrast to the marked long-range hexagonal ordering seen in experiments. However, the scaling behavior is robust enough that roughening kinetics similar to that observed experimentally can be obtained depending upon the values of inhomogeneity and the strength of the nonlinear term in the model.

Dynamical scaling of sputter-roughened surfaces in 2+1 dimensions.

The asymptotic scaling behavior of sputter-roughened surfaces is of great current interest. In particular, the disparately wide-ranging values of the growth exponent found experimentally, and whether sputter-roughening belongs to the Kardar-Parisi-Zhang universality class in 2+1 dimensions, are two interesting issues. We address these issues using simulations of an atomistic model. The asymptotic scaling appears to be Edwards-Wilkinson. Crossover behavior in the model leads to effective growth exponents that vary widely depending upon the regime of observation.

Hydrogen desorption kinetics from the Si(1-x)Gex(100)-(2x1) surface.

We study the influence of germanium atoms upon molecular hydrogen desorption energetics using density functional cluster calculations. A three-dimer cluster is used to model the Si((1-x))Ge(x)(100)-(2x1) surface. The relative stabilities of the various monohydride and clean surface configurations are computed. We also compute the energy barriers for desorption from silicon, germanium, and mixed dimers with various neighboring configurations of silicon and germanium atoms. Our results indicate that there are two desorption channels from mixed dimers, one with an energy barrier close to that for desorption from germanium dimers and one with an energy barrier close to that for desorption from silicon dimers. Coupled with the preferential formation of mixed dimers over silicon or germanium dimers on the surface, our results suggest that the low barrier mixed dimer channel plays an important role in hydrogen desorption from silicon-germanium surfaces. A simple kinetics model is used to show that reasonable thermal desorption spectra result from incorporating this channel into the mechanism for hydrogen desorption. Our results help to resolve the discrepancy between the surface germanium coverage found from thermal desorption spectra analysis, and the results of composition measurements using photoemission experiments. We also find from our cluster calculations that germanium dimers exert little influence upon the hydrogen desorption barriers of neighboring silicon or germanium dimers. However, a relatively larger effect upon the desorption barrier is observed in our calculations when germanium atoms are present in the second layer.