Scientific Publications 2010
2010. "Epitaxial Growth and Orientational Dependence of Surface Photochemistry in CrystallineTiO2 Rutile Films Doped with Nitrogen." Journal of Physical Chemistry C 114(14):6595-6601. doi:10.1021/jp1002726 Abstract We have prepared and investigated the structural, compositional, morphological and photochemical properties of N-doped TiO2(110), (100) and (001) epitaxial films grown by means of plasma-assisted molecular beam epitaxy. The N solid solubility is limited to ~ 1 at. % of the total anions in the lattice in films where excellent long-range structural order is maintained throughout growth. The photochemical activity of the resulting surfaces was evaluated using hole-mediated decomposition of adsorbed trimethyl acetate. Undoped surfaces of the three orientations exhibited comparable photochemical activities. However, the dependence of the photochemical activity on N concentration shows a marked crystallographic dependence. The results are rationalized in terms of the apparent crystallographic anisotropy of hole mobility as well as hole trapping and detrapping probabilities.
2010. "CO activation pathways and the mechanism of Fischer–Tropsch synthesis." Journal of Catalysis 272(2):287-297. doi:10.1016/j.jcat.2010.04.012 Abstract Unresolved mechanistic details of monomer formation in Fischer–Tropsch synthesis (FTS) and of its oxygen rejection routes are addressed here by combining kinetic and theoretical analyses of elementary steps on representative Fe and Co surfaces saturated with chemisorbed CO. These studies provide experimental and theoretical evidence for hydrogen-assisted CO activation as the predominant kinetically-relevant step on Fe and Co catalysts at conditions typical of FTS practice. H2 and CO kinetic effects on FTS rates and oxygen rejection selectivity (as H2O or CO2) and density functional theory estimates of activation barriers and binding energies are consistent with H-assisted CO dissociation, but not with the previously accepted kinetic relevance of direct CO dissociation and chemisorbed carbon hydrogenation elementary steps. H-assisted CO dissociation removes O-atoms as H2O, while direct dissociation forms chemisorbed oxygen atoms that desorb as CO2. Direct CO dissociation routes are minor contributors to monomer formation on Fe and may become favored at high temperatures on alkali-promoted catalysts, but not on Co catalysts, which remove oxygen predominantly as H2O because of the preponderance of Hassisted CO dissociation routes. The merging of experiment and theory led to the clarification of persistent mechanistic issues previously unresolved by separate experimental and theoretical inquiries.
2010. "Kinetically Relevant Steps and H2/D2 Isotope Effects in Fischer-Tropsch Synthesis on Fe and Co Catalysts." Journal of Physical Chemistry C 114(46):19761-19770. doi:10.1021/jp1073076 Abstract H2/D2 isotope effects on Fischer-Tropsch synthesis (FTS) rate and selectivity are examined here by combining measured values on Fe and Co at conditions leading to high C5+ yields with theoretical estimates on model Fe(110) and Co(0001) surfaces with high coverages of chemisorbed CO (CO*). Inverse isotope effects (rH/rD < 1) are observed on Co and Fe catalysts as a result of compensating thermodynamic (H2 dissociation to H*; H* addition to CO* species to form HCO*) and kinetic (H* reaction with HCO*) isotope effects. These isotopic effects and their rigorous mechanistic interpretation confirm the prevalence of H-assisted CO dissociation routes on both Fe and Co catalysts, instead of unassisted pathways that would lead to similar rates with H2 and D2 reactants. The small contributions from unassisted pathways to CO conversion rates on Fe are indeed independent of the dihydrogen isotope, as is also the case for the rates of primary reactions that form CO2 as the sole oxygen rejection route in unassisted CO dissociation paths. Isotopic effects on the selectivity to C5+ and CH4 products are small, and D2 leads to a more paraffinic product than does H2, apparently because it leads to preference for chain termination via hydrogen addition over abstraction. These results are consistent with FTS pathways limited by H-assisted CO dissociation on both Fe and Co and illustrate the importance of thermodynamic contributions to inverse isotope effects for reactions involving quasi-equilibrated H2 dissociation and the subsequent addition of H* in hydrogenation catalysis, as illustrated here by theory and experiment for the specific case of CO hydrogenation.
2010. "Determination of Electric-Field, Magnetic-Field, and Electric-Current Distributions of Infrared Optical Antennas: A Near-Field Optical Vector Network Analyzer." Physical Review Letters 105(16):Article No.: 167403. doi:10.1103/PhysRevLett.105.167403 Abstract In addition to the electric field E(r), the associated magnetic field H(r) and current density J(r) characterize any electromagnetic device, providing insight into antenna coupling and mutual impedance. We demonstrate the optical analogue of the radio frequency vector network analyzer implemented in interferometric homodyne scattering-type scanning near-field optical microscopy (s-SNOM) for obtaining E(r), H(r), and J(r). The approach is generally applicable and demonstrated for the case of a linear coupled-dipole antenna in the midinfrared. The determination of the underlying 3D vector electric near-field distribution E(r) with nanometer spatial resolution and full phase and amplitude information is enabled by the design of probe tips with selectivity with respect to Ek and E? fabricated by focused ion-beam milling and nano-CVD.
2010. "Three-Dimensional Simulation of Volatile Organic Compound Mass Flux from the Vadose Zone to Groundwater ." Ground Water Monitoring and Remediation 30(3):45-56. Abstract Low permeability layers of the vadose zone containing volatile organic compounds (VOCs) may persist as source zones for long time periods and may provide contamination to groundwater. At sites with low recharge rates, where vapor migration is the dominant transport process, the impact of vadose zone sources on groundwater may be difficult to assess. Typical assessment methods include one-dimensional numerical and analytical techniques. The one-dimensional approaches only consider groundwater coupling options through boundary conditions at the water table and may yield artificially high mass flux results when transport is assumed to occur by gas-phase diffusion between a source and an interface with a zero concentration boundary condition. Improvements in mass flux assessments for VOCs originating from vadose zone sources may be obtained by coupling vadose zone gas transport and dissolved contaminant transport in the saturated zone and by incorporating the inherent three-dimensional nature of gas-phase transport, including the potential of density-driven advection. This paper describes a series of three-dimensional simulations using data from the U.S. Department of Energy’s Hanford Site, where carbon tetrachloride is present in a low permeability zone about 30 m above the groundwater. Results show that, for most cases, only a relatively small amount of the contaminant emanating from the source zone partitions into the groundwater and that density-driven advection is only important when relatively high source concentrations are considered.
2010. "Modeling aerosol growth by aqueous chemistry in nonprecipitating stratiform cloud." Journal of Geophysical Research. D. (Atmospheres) 115(D14210):, doi:10.1029/2009JD012816 Abstract A new microphysics module based on a two-dimensional (2D) joint size distribution function representing both interstitial and cloud particles is developed and applied to studying aerosol processing in non-precipitating stratocumulus clouds. The module is implemented in a three-dimensional dynamical framework of a large-eddy simulation (LES) model and in a trajectory ensemble model (TEM). Both models are used to study the modification of sulfate aerosol by the activation - aqueous chemistry - resuspension cycle in shallow marine stratocumulus clouds. The effect of particle mixing and different size-distribution representations on modeled aerosol processing are studied in a comparison of the LES and TEM simulations with the identical microphysics treatment exposes and a comparison of TEM simulations with a 2D fixed and moving bin microphysics. Particle mixing which is represented in LES and neglected in the TEM leads to the mean relative per particle dry mass change in the TEM simulations being about 30% lower than in analogous subsample of LES domain. Particles in the final LES spectrum are mixed in from different “parcels”, some of which have experienced longer in-cloud residence times than the TEM parcels, all of which originated in the subcloud layer, have. The mean relative per particle dry mass change differs by 14% between TEM simulations with fixed and moving bin microphysics. Finally, the TEM model with the moving bin microphysics is used to evaluate assumptions about liquid water mass partitioning among activated cloud condensation nuclei (CCN) of different dry sizes. These assumptions are used in large-scale models to map the bulk aqueous chemistry sulfate production, which is largely proportional to the liquid water mass, to the changes in aerosol size distribution. It is shown that the commonly used assumptions that the droplet mass is independent of CCN size or that the droplet mass is proportional to the CCN size to the third power do not perform well in the considered case. The explicitly predicted water partitioning indicates that the mean mass of droplets participating in the models aqueous chemistry calculations is proportional to the dry CCN size.