Planar oxide supported rhodium nanoparticles as model catalysts.

C(2)H(4)/CO/H(2) reaction is investigated on Rh/SiO(2) model catalyst surfaces. Kinetic reactivity and infrared spectroscopic measurements are investigated as a function of Rh particle size under near atmospheric reaction conditions. Results show that propionaldehyde turnover frequency (TOF) (CO insertion pathway) exhibits a maximum activity near = 2.5 nm. Polarization modulation infrared reflection absorption spectroscopy under CO and reaction (C(2)H(4)/CO/H(2)) conditions indicate the presence of Rh carbonyl species (Rh(CO)(2), Rh(CO)H) on small Rh particles, whereas larger particles appear resistant to dispersion and carbonyl formation. Combined these observations suggest the observed particle size dependence for propionaldehyde production via CO insertion is driven by two factors: (i) an increase in propionaldehyde formation on undercoordinated Rh sites and (ii) creation of carbonyl hydride species (Rh(CO)H)) on smaller Rh particles, whose presence correlates with the lower activity for propionaldehyde formation for < 2.5 nm.

Structural, compositional and electrochemical characterization of Pt-Co oxygen-reduction catalysts.

Pt-Co thin-film electrocatalysts have been characterized using low-energy ion-scattering spectroscopy (LEISS), X-ray photoelectron spectroscopy (XPS), low-energy electron diffraction (LEED), temperature-programmed desorption (TPD) and electrochemistry (EC). For comparative purposes, LEISS and EC were also carried out on a bulk Pt(3)Co(111) single crystal. The extensive experimental work resulted in the establishment of the surface phase diagram of the alloy film marked by a substantial divergence between the composition at the interface and that in the interior. When a dual-layer deposit of Pt and Co was annealed at high temperatures, alloy formation transpired in which the outermost layer became single-crystalline and enriched in Pt. The preferential surface segregation of Pt, however, was not sufficient to generate a platinum-only overlayer or "skin". Invariably, Co was found to co-exist with Pt, independent of the substrate [Mo(110) or Ru(0001)] employed; Pt(3)Co was the most favored composition. The same result, the absence of a Pt skin, was likewise indicated at the post-thermally-annealed surface of the bulk Pt(3)Co(111) monocrystal. For alloy-film surfaces more enriched in Pt than Pt(3)Co, the topmost layer was constituted primarily, but not exclusively, of Pt(111) domains. The proclivities of the alloys towards enhanced catalysis of the oxygen-reduction reaction were assessed in terms of their voltage efficiencies, as manifested by the open-circuit potential (OCP) in O(2)-saturated sulfuric acid electrolyte. The Pt(3)Co surface, whether from the thin film or the bulk single crystal, exhibited the highest OCP, a significant improvement over pure Pt but still appreciably lower than the thermodynamic limit. The degradation of the Pt(3)Co thin-film surface was predominantly due to Co corrosion. A minimal amount was spontaneously dissolved upon simple immersion in solution; slightly higher dissolution occurred at potentials above the OCP. The fraction that was not immediately corroded proved to be stable even after prolonged periods at potentials more positive than the OCP.

Characterization of active sites on Rh/SiO(2) model catalysts.

Rh/SiO(2) model catalyst surfaces are prepared under ultra-high vacuum conditions and examined in situ using scanning tunneling microscope and CO infrared reflection absorption techniques, to quantify the number and kinds of active Rh surface sites available for kinetic reaction (CO oxidation) as a function of Rh particle size. The results are compared against CO desorption measurements and elevated pressure CO oxidation reaction kinetics, to evaluate the extent of the correlation between the low and elevated pressure site characterization techniques. Data demonstrate that estimates of Rh active sites exhibit good agreement between the characterization methods and illustrate the utility of low pressure surface science characterization techniques in understanding elevated pressure reaction kinetics on model catalyst surfaces.

Ultrathin, ordered oxide films on metal surfaces.

Metal oxides and oxide thin films are extensively used as active catalysts and catalytic supports, as well as in many other important technical applications. Unlike TiO(2), which is a semiconductor and can be investigated using a variety of surface science techniques, most metal oxides are insulators, which seriously restricts their use as model surfaces with modern surface science techniques. This difficulty can be circumvented by synthesizing ultrathin oxide films a few nanometers in thickness with well-defined structures, that mimic the corresponding bulk oxides yet are thin enough to be sufficiently conducting. In this review, preparations, structures, electronic and chemical properties of four representative oxides, alumina, magnesium oxide, silica, and titania, are addressed. Of these MgO is found to grow in a layer-by-layer fashion, allowing preparation of crystalline thin film structures with varying thicknesses. Crystalline TiO(2) and Ti(2)O(3) can also be synthesized, whereas SiO(2) and Al(2)O(3), although amenable to synthesis as well-defined monolayer structures, have only been grown to date as amorphous multilayers.

NO adsorption and dissociation on Rh(111): PM-IRAS study.

We have used in situ polarization-modulation infrared reflection absorption spectroscopy to study the adsorption/dissociation of NO on Rh(111). While these studies have not been conclusive regarding the detailed surface structures formed during adsorption, they have provided important new information on the dissociation of NO on Rh(111). At moderate pressures (< or =10(-6) Torr) and temperatures (<275 K), a transition from 3-fold hollow to atop bonding is apparent. Data indicate that this transition is not due to the migration of the 3-fold hollow NO but rather to the adsorption of gas-phase NO that is directed toward the atop position due to the presence of NO decomposition products, particularly chemisorbed atomic O species at the hollow sites. These results indicate that NO dissociation occurs at temperatures well below the temperature previously reported. Additionally, high pressure (1 Torr) NO exposure at 300 K results in only atop NO, calling into question the surface structures previously proposed at these adsorption conditions consisting of atop and 3-fold hollow sites.

Preparation and characterization of silica supported Au-Pd model catalysts.

Au-Pd bimetallic model catalysts were synthesized as alloy clusters on SiO2 ultrathin films under ultrahigh vacuum (UHV) conditions. The surface composition and morphology were characterized with low energy ion scattering spectroscopy (LEIS), infrared reflection absorption spectroscopy (IRAS), and temperature programmed desorption (TPD). Relative to the bulk, the surface of the clusters is enriched in Au. With CO as a probe, IRAS and TPD were used to identify isolated Pd sites at the surface of the supported Au-Pd clusters. Ethylene adsorption and dehydrogenation show a clear structure-reactivity correlation with respect to the structure/composition of these Au-Pd model catalysts.

CO-NO and CO-O(2) interactions on Cu(100) between 25 and 200 K studied with infrared reflection absorption spectroscopy.

Infrared reflection absorption spectroscopy (IRAS) has been used to study CO-NO and CO-O(2) interactions on Cu(100) between 25 and 200 K. A strong repulsive interaction between CO and NO on Cu(100) at 25 K causes tilting of the CO molecules away from the surface normal and a blue-shift of the CO vibrational frequency. Upon warming and decomposition of the NO, the CO molecules return to a bonding position normal to the surface plane. The vibrational frequency of CO blue-shifts from 2087 to 2136 cm(-1) upon coadsorption with N and O atoms formed from NO decomposition. On the other hand, the interaction of CO with O(2) at 27 K on Cu(100) in the submonolayer regime induces a red-shift of the CO vibrational frequency. Atomic oxygen, formed on Cu(100) by dissociation of O(2) at 95 K, induces a blue-shift of the vibrational frequency of coadsorbed CO to 2116 cm(-1). The CO vibrational frequency shifts to 2091 cm(-1) when the surface is annealed to 140 K, implying a change in the adsorption geometry of the oxygen atoms on Cu(100).

The growth of silver on an ordered alumina surface.

The growth of Ag on an ordered Al2O3 surface was studied by low energy ion scattering spectroscopy (LEIS), scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD). Three-dimensional (3D) growth of Ag clusters was observed with STM and LEIS, with the cluster size increasing with Ag coverage. The XPS core level binding energies and the Auger parameters indicate a weak interaction between the Ag clusters and the Al2O3 support. Final state effects are determined to be the primary contribution to the Ag core level binding energy shift. Nonzero order kinetics was observed for Ag desorption in TPD with the Ag sublimation energy decreasing with decreasing cluster size.

The composition and structure of Pd-Au surfaces.

Pd, Au, and Pd-Au mixtures were deposited via physical vapor deposition onto a Mo(110) substrate, and the surface concentration and morphology of the Pd-Au mixtures were determined by low-energy ion scattering spectroscopy (LEISS), infrared absorption spectroscopy (IRAS), temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). Pd-Au mixtures form a stable alloy between 700 and 1000 K with substantial enrichment in Au compared to the bulk composition. Annealing a 1:1 Pd-Au mixture at 800 K leads to the formation of a surface alloy with a composition Au(0.8)Pd(0.2) where Pd is predominantly surrounded by Au. The surface concentration of this isolated Pd site can be systematically controlled by altering the bulk Pd-Au alloy concentration.

The structure of catalytically active gold on titania.

The high catalytic activity of gold clusters on oxides has been attributed to structural effects (including particle thickness and shape and metal oxidation state), as well as to support effects. We have created well-ordered gold mono-layers and bilayers that completely wet (cover) the oxide support, thus eliminating particle shape and direct support effects. High-resolution electron energy loss spectroscopy and carbon monoxide adsorption confirm that the gold atoms are bonded to titanium atoms. Kinetic measurements for the catalytic oxidation of carbon monoxide show that the gold bilayer structure is significantly more active (by more than an order of magnitude) than the monolayer.

In situ scanning tunneling microscopy of oxide-supported metal clusters: nucleation, growth, and thermal evolution of individual particles.

An experimental approach was developed for imaging the nucleation and growth of individual oxide-supported nanoparticles and their subsequent in situ chemical and thermal treatments by scanning tunneling microscopy (STM). The potential of the method is demonstrated for Au nanoparticles supported on a reduced TiO(2) substrate where a cluster-by-cluster comparison is made of the morphological evolution and stability of nanoparticles during their nucleation and thermal annealing. Using this methodology the details of the nucleation and growth kinetics can be directly observed.

Catalysis research of relevance to carbon management: progress, challenges, and opportunities.

The goal of the "Opportunities for Catalysis Research in Carbon Management" workshop was to review within the context of greenhouse gas/carbon issues the current state of knowledge, barriers to further scientific and technological progress, and basic scientific research needs in the areas of H2 generation and utilization, light hydrocarbon activation and utilization, carbon dioxide activation, utilization, and sequestration, emerging techniques and research directions in relevant catalysis research, and in catalysis for more efficient transportation engines. Several overarching themes emerge from this review. First and foremost, there is a pressing need to better understand in detail the catalytic mechanisms involved in almost every process area mentioned above. This includes the structures, energetics, lifetimes, and reactivities of the species thought to be important in the key catalytic cycles. As much of this type of information as is possible to acquire would also greatly aid in better understanding perplexing, incomplete/inefficient catalytic cycles and in inventing new, efficient ones. The most productive way to attack such problems must include long-term, in-depth fundamental studies of both commercial and model processes, by conventional research techniques and, importantly, by applying various promising new physicochemical and computational approaches which would allow incisive, in situ elucidation of reaction pathways. There is also a consensus that more exploratory experiments, especially high-risk, unconventional catalytic and model studies, should be undertaken. Such an effort will likely require specialized equipment, instrumentation, and computational facilities. The most expeditious and cost-effective means to carry out this research would be by close coupling of academic, industrial, and national laboratory catalysis efforts worldwide. Completely new research approaches should be vigorously explored, ranging from novel compositions, fabrication techniques, reactors, and reaction conditions for heterogeneous catalysts, to novel ligands and ligation geometries (e.g., biomimetic), reaction media, and activation methods for homogeneous ones. The interplay between these two areas involving various hybrid and single-site supported catalyst systems should also be productive. Finally, new combinatorial and semicombinatorial means to rapidly create and screen catalyst systems are now available. As a complement to the approaches noted above, these techniques promise to greatly accelerate catalyst discovery, evaluation, and understanding. They should be incorporated in the vigorous international research effort needed in this field.

Determination of trans-resveratrol in human plasma by high-performance liquid chromatography.

The first method using high-performance liquid chromatography (HPLC) has been developed for the determination of trans-resveratrol in human plasma. The method involves a liquid--liquid extraction followed by reversed-phase HPLC with UV detection. The detection limit of trans-resveratrol in human plasma was 5.0 ng/ml. Standard curves are linear over the concentration range of 5.0-5000.0 ng/ml. Intra-assay variability ranged from 1.9 to 3.7% and inter-assay variability ranged from 2.5 to 4.0% at the concentration range of 15.0-4000.0 ng/ml.

Calcium Phosphate Phase Identification Using XPS and Time-of-Flight Cluster SIMS.

Reproducible time-of-flight cluster static secondary ion mass spectra (ToF-SSIMS) were obtained for various standard calcium phosphate (CP) powders, which allowed for phase identification. X-ray diffraction was not able to detect signals from microscopic amounts of CP (∼15 mmol m(-)(2)). The phases studied were α-tricalcium phosphate [α-Ca(3)(PO(4))(2)], ß-tricalcium phosphate [ß-Ca(3)(PO(4))(2)], amorphous calcium phosphate [Ca(3)(PO(4))(2)·xH(2)O], octacalcium phosphate [Ca(8)H(2)(PO(4))(6)·H(2)O], brushite (CaHPO(4)·2H(2)O), and hydroxyapatite [Ca(10)(PO(4))(6)(OH)(2)]. The SIMS spectra were obtained via bombardment with (CsI)Cs(+) projectiles. X-ray photoelectron spectroscopy (XPS) core levels of the P 2p, Ca 2p, and O 1s orbitals and the relative O 1s loss intensity were examined. The PO(3)(-)/PO(2)(-) ratios from ToF-SSIMS spectra in conjunction with XPS of the CP powders showed much promise in differentiating between these phases at microscopic CP coverages on the metal oxide surface.

The physical and chemical properties of ultrathin oxide films.

Thin oxide films (from one to tens of monolayers) of SiO2, MgO, NiO, Al2O3, FexOy, and TiO2 supported on refractory metal substrates have been prepared by depositing the oxide metal precursor in a background of oxygen (ca 1 x 10(-5) Torr). The thinness of these oxide samples facilitates investigation by an array of surface techniques, many of which are precluded when applied to the corresponding bulk oxide. Layered and mixed binary oxides have been prepared by sequential synthesis of dissimilar oxide layers or co-deposition of two different oxides. Recent work has shown that the underlying oxide substrate can markedly influence the electronic and chemical properties of the overlayer oxide. The structural, electronic, and chemical properties of these ultrathin oxide films have been probed using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), electron energy loss spectroscopy (ELS), ion-scattering spectroscopy (ISS), high-resolution electron energy loss spectroscopy (HREELS), infrared reflectance absorption spectroscopy (IRAS), temperature-programmed desorption (TPD), scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS).

New segregation analysis of panic disorder.

We performed simple segregation analyses of panic disorder using 126 families of probands with DSM-III-R panic disorder who were ascertained for a family study of anxiety disorders at an anxiety disorders research clinic. We present parameter estimates for dominant, recessive, and arbitrary single major locus models without sex effects, as well as for a nongenetic transmission model, and compare these models to each other and to models obtained by other investigators. We rejected the nongenetic transmission model when comparing it to the recessive model. Consistent with some previous reports, we find comparable support for dominant and recessive models, and in both cases estimate nonzero phenocopy rates. The effect of restricting the analysis to families of probands without any lifetime history of comorbid major depression (MDD) was also examined. No notable differences in parameter estimates were found in that subsample, although the power of that analysis was low. Consistency between the findings in our sample and in another independently collected sample suggests the possibility of pooling such samples in the future in order to achieve the necessary power for more complex analyses.

On estimation of linkage test power.

Two methods of estimating linkage test power are proposed. The first method is based on the maximum likelihood (ML) estimate of the recombination fraction and is intended for use with a likelihood ratio test (LRT) in the form of a chi 2 or lod score. The power is estimated through a noncentral chi 2 distribution with a specially chosen noncentrality parameter. The second method uses the LRT constructed for a simple alternative hypothesis regarding the recombination fraction value. The approximate distribution of this test and a method of estimating its power is proposed. Using simulated pedigree data, the power estimates for these two methods were shown to be satisfactory. Comparisons among these two methods and the computer simulation approach of Boehnke [1986] are performed.

Antibody binding to the juxtamembrane region of the insulin receptor alters receptor affinity.

The effect of three antibodies that interact with distinct regions of the insulin receptor (the alpha subunit (83-7), the juxtamembrane region near tyrosine 960 (960) or the carboxy terminal region of the beta subunit (CT-1) on insulin binding was examined. Detergent-solubilized insulin receptors from IM-9 cells immobilized on Sepharose beads by 960 antisera bound 2-3 times more 125I-insulin tracer (25-60 pM) than receptors immobilized with either 83-7 or CT-1. Pre-incubation of solubilized receptors with either 83-7 or 960 resulted in equivalent depletion (90%) of insulin binding activity from solubilized IM-9 cell extracts, suggesting that both antibodies were in excess and capable of binding a similar population of receptors. Antibody 960, but not CT-1 or 83-7, also increased insulin binding 2 fold to solubilized receptors precipitated with polyethylene glycol. To determine whether the altered binding observed with antibody 960 was due to increased affinity of the receptor for insulin or appearance of more insulin binding sites, binding studies were performed over a wide range of insulin concentrations. Analysis of the resulting binding curves indicated that 960 increased the affinity of the receptor for insulin 3 fold over control (kd = 0.3 nM for 960, and 0.9 nM for 83-7, respectively). The antibody 960 also specifically increased insulin binding to intact, saponin-permeabilized IM-9 cell membranes. These results indicate that binding of 960 antibody to the juxtamembrane region of the insulin receptor alters the affinity of the receptor for insulin. Since tyrosine 960 in the juxtamembrane region has been suggested to play a role in receptor signalling, changes in receptor conformation in this region that are likely to account for the change in affinity may play a role in signal transduction.

Mitogen activation of resting lymphocytes exposes cryptic insulin receptors.

Mitogen activation of resting lymphocytes induces expression of high affinity insulin receptors on the plasma membrane. The mechanism underlying this effect on insulin receptor expression was examined by comparing levels of insulin receptor mRNA and protein in resting and mitogen-activated rodent lymphocytes. Analysis of RNA levels indicated that resting and concanavalin A-activated lymphocytes contained equivalent amounts of insulin receptor mRNA with predominant transcripts of 7.9 and 9.5 kilobases. Although little or no insulin binding was detectable on intact resting lymphocytes, detergent solubilization of these cells resulted in the appearance of readily detectable insulin binding activity that could be immunoprecipitated with anti-insulin receptor antibodies. Detergent-solubilized resting and mitogen-activated lymphocytes expressed equivalent amounts of insulin receptors that bound insulin with similar affinity (KD = 90 pM) and migrated on reduced SDS-polyacrylamide gels with apparent masses of approximately 130 and approximately 95 kDa. Insulin receptors from resting lymphocytes appeared to be associated with the plasma membrane since 125I labeling of intact lymphocytes radiolabeled the insulin receptor, insulin binding activity was detected in membrane fractions of hypotonically lysed cells, and trypsin treatment of intact cells destroyed > 90% of the insulin binding activity in detergent extracts. These results suggest that resting lymphocytes express insulin receptor mRNA and protein and that mitogen activation exposes cryptic insulin receptors present in the plasma membrane of resting lymphocytes.